CN111073014A - Degradable film with enhanced water-oxygen barrier performance by physical deposition - Google Patents
Degradable film with enhanced water-oxygen barrier performance by physical deposition Download PDFInfo
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Abstract
The invention discloses a structure and a preparation process of a degradable film with high water oxygen barrier performance, which can meet the requirements of high-performance water oxygen barrier packaging of various ultrathin and flexible electronic devices, medical treatment, biology and the like, and particularly realizes the function of enhancing ultrahigh water oxygen barrier of the degradable film by realizing the design and the technology of combining a nanometer film layer and the degradable film through a physical deposition technology.
Description
Technical Field
The invention belongs to the technical field of research of novel environment-friendly materials, and particularly relates to a degradable film with enhanced water-oxygen barrier performance by physical deposition.
Background
With the new materials, new technologies, and rapid upgrade and upgrade of new products in the electronics industry, many new microelectronic devices are emerging in our lives, including the rapidly developing flexible electronics industry, printable electronics, electromechanical electronic devices, bioelectronics, thin film electronics industry, and the like. These new industries change our lives, works, and our future. For example: the foldable screen mobile phone, the curved surface television and other display and solid-state lighting, energy, detectors, notebooks, medical instruments and food detection based future wearable fields have wide application prospects. These novel technologies have outstanding features such as ultra-thinness, photoelectric properties, flexibility, and the like. Will be the core or key technology of many future, next generation electronic, information technology. Its development has received the attention and great investment of all developed countries, international companies. As one of the important basic materials, flexible, high water oxygen barrier films are one of the important developments, and only a few companies in the world have advanced technologies.
While we are developing new thin film encapsulation materials and techniques, we have to face an important problem. Electronic waste and plastic waste harm the development and stability of our whole earth and human society. On the basis of the effort of improving the living standard and the technical level of human beings, people also pay attention to the problems of environment, environmental protection and garbage. Cannot develop a new technology, and causes harm to the environment and the ecology, and the social benefit and the economic benefit of the technology are greatly reduced. As the field of packaging films at present, the dilemma is faced, on one hand, the high-performance water-oxygen barrier film is difficult to degrade by nature and is integrated with electronic products. Becomes a new product which is difficult to recycle and utilize and has great harm to the environment.
With the development of many biological and materials industries, biodegradable or environmentally friendly plastics, film materials are being developed and are beginning to be used in our lives. Is used for replacing the existing non-degradable and environment-friendly plastic products. Whether these materials and films can be applied or not, a novel high water oxygen barrier film is developed. Meanwhile, the packaging material has the water oxygen barrier property meeting the high packaging requirement, is degradable, and has the double advantages of environment friendliness and recyclable packaging. It is necessary to upgrade and develop new processes and technologies to solve the problems in the prior art. First, compare to conventional plastic films. Degradable films are inferior in physical properties and water oxygen barrier properties. Further improvements and optimizations are needed compared to the high water oxygen barrier technology in conventional plastic films. For example, the degradable material has the problems of overlarge fiber, uneven film, dispersed surface thickness, large space in the film, difficult overhigh temperature and the like.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
The invention aims to design a degradable packaging film which is novel water-oxygen barrier and is prepared by preparing a high-density nano layer or a UV acrylic resin protective layer on a degradable film by means of a physical deposition technology.
A degradable film with enhanced water-oxygen barrier performance through physical deposition comprises a degradable film, an inorganic nano protective layer physically deposited on the surface of the degradable film, and acrylic resin coated and photocured on the surface of the inorganic nano protective layer.
The problem that a plurality of plastic films used in the packaging process of the current flexible electronic device are not friendly to the environment and are novel plastic pollution sources is solved. The basic principle of the invention is that dense nanometer metal, inorganic atoms and molecules are partially covered on the upper part of degradable organic molecules by utilizing a mild and precise physical deposition technology, and are partially filled among the molecules to form a dense nanometer barrier layer, and then the nanometer barrier layer and the degradable film can be protected and covered by a UV curing material. The plastic film prepared by the method not only has high water oxygen barrier property, but also greatly reduces the pressure and pollution to the environment. Meanwhile, the requirements of high performance of flexible electronic packaging and the requirements of environmental protection technology are met. The application range and long-term planning of the high water oxygen barrier film can be greatly improved. The high water oxygen barrier film can be applied to the substrate of flexible electronic products and can also be applied to the packaging process of the products. And the degradable film has the characteristics of environmental protection and health, and can be even applied to the fields with high sealing requirements of various medicines, organisms, preparations, foods and the like. The patent designs optimizes the preparation process and scheme of the degradable film in consideration of the stability in preparation of the nano layer. The problem of poor water oxygen barrier property of the original degradable material is solved from the design and preparation of the nano protective layer.
Preferably, in the above technical solution, the degradable material film is made of a material selected from PLA, PHA, PBAS, PPC, PVA, PHB, PBS, and bioengineering plastics, bio-versatile plastics (polyolefin and polyvinyl chloride) starch base, and the like.
Preferably, in the above technical solution, the degradable material film is selected from a single-layer or multi-layer mixed degradable material structure, and the thickness of the degradable material film is in a range of 5 micrometers to 500 micrometers.
Preferably, in the above technical solution, the inorganic nano protective layer may be made of a material selected from metals, metal oxides and inorganic nano materials, and has a thickness of 10-500 nm.
Preferably, in the above technical solution, the inorganic nano-protection layer may be a single nano-material layer, or may be a mixed layer of multiple nano-materials.
Preferably, in the above technical solution, the thickness of the UV-curable acrylic resin layer is between 0.1 and 50 μm.
A preparation process of a degradable film with enhanced water-oxygen barrier performance by physical deposition comprises the following steps: the surface treatment is carried out on the ultrathin degradable film, the nano-scale compact barrier layer is deposited by a physical deposition technology, then the UV curing acrylic resin can be coated on the upper part, and the curing protection is finished after the UV irradiation, or the curing layer is not needed.
Preferably, in the above technical solution, the surface treatment of the degradable material film may be selected from ozone, plasma, chemical, corona and other methods.
Preferably, in the above technical solution, the physical deposition technique can be RF, DC or magnetron sputtering, vacuum evaporation, low pressure evaporation, arc plasma plating, ion plating, molecular beam epitaxy, and the like.
Preferably, in the above technical scheme, the temperature of the degradable film can be kept within a range from room temperature to 80 ℃ by a physical deposition technology, and the coating rate is 1-50 nm/min.
The film preparation process is established on a high-efficiency physical deposition nano barrier layer and is combined with the advantages of a degradable film or a curable acrylic resin, the water oxygen barrier property of the original degradable film or material is improved by 3-6 orders of magnitude again by utilizing the coating of a single-layer or multi-layer nano compact layer, and the disadvantages and shortcomings of the degradable film on the water oxygen barrier property are greatly improved. So that the degradable film also has the similar water and oxygen barrier performance as the traditional and commercialized plastic film. Due to the high water oxygen barrier performance, the degradable film and the plastic have the prospect and potential of application in the field with high packaging requirements. Although the traditional and existing plastic and polymer films have mature technical schemes and higher water-oxygen barrier performance, the development of the films in the fields of flexibility and film electronics is also restricted by the essential environmental protection problem. It causes many social and industrial problems such as environmental, recycling, disposal, etc: for example: 1. and meanwhile, new electronic garbage and plastic garbage are generated, and 2. different plastics and electronic products are difficult to uniformly recover and separate. 3 adding new difficulties to the existing waste recovery and sorting. The new plastic/polymer brings the advantages of the plastic/polymer into the electronic industry and also brings the problems of environmental protection, difficult recycling and the like. For example, many flexible electronic devices are now scrapped and recycled with higher requirements for cost, means and technology, and consumers are plagued by new garbage and environmental problems while enjoying new products. If environmental protection materials are introduced early on the material level or new packaging and high-water-oxygen-barrier degradation films are developed, the damage to the environment and the society can be reduced from the beginning. The invention effectively deposits a compact nano layer on the degradable film by utilizing a physical deposition scheme, thereby greatly reducing water molecules and oxygen molecules passing through a channel of a gap between degradable macromolecules. Even a method of multilayer deposition coating or mixed coating is utilized to further improve the water and oxygen barrier performance, thereby obtaining the water and oxygen barrier performance far exceeding the water and oxygen barrier performance of the original degradable film. Due to the nano-physical deposition technique adopted, the method can also be combined with UV curing acrylic resin for use: the nano layer can be coated with acrylic resin, and a film product with better water and oxygen barrier property and durability can be obtained after curing. The composite film is suitable for replacing some high-performance water-oxygen-barrier non-degradable plastic films and is applied to the field of packaging of sensitive materials such as flexible electronic device packaging, medicine packaging, food and the like. The invention innovatively provides a new design and preparation process scheme of an environment-friendly packaging film, and the nano-layer coating and the organic degradation film are combined with coating technologies such as curing resin and the like. Although the process is special, the advantages of the physical properties and the encapsulation properties of the two materials can be integrated, and the encapsulation performance and the application stability of the degradable material can be greatly improved.
The mild physical deposition scheme near room temperature effectively deposits the compact nano layer in the degradable film, effectively fills gaps among molecules and achieves the purpose of improving the water oxygen barrier performance. Compared with the published technology, the technology has the advantages that the preparation, compactness, uniformity and reliability of the nanometer compact layer are greatly improved, and the technology has the following requirements:
A. the degradable film is stable and lossless in the preparation process of the nano layer.
B. The degradable film has no degradation in the real process.
C. The compact nano layer has a certain speed in molecular growth and can be uniformly covered on and in the molecule of the degradable material.
D. The dense nano-layer should be metal, oxide, inorganic substance, etc. with atomic or molecular diameter less than 1 nanometer to block water and oxygen molecules efficiently.
E. The final nanolayer may be protected by a UV cured layer.
Description of the drawings:
FIG. 1 is a schematic flow diagram of the present invention;
FIG. 2 is a schematic structural view of the present invention;
in the figure: 1. degradable film, 2, degradable film surface treatment and cleaning, 3, inorganic nano protective layer, 4, covering light-cured acrylic resin.
The specific implementation mode is as follows:
the following detailed description of specific embodiments of the invention is provided, but it should be understood that the scope of the invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
A degradable film with enhanced water-oxygen barrier performance through physical deposition comprises a degradable film, an inorganic nano protective layer physically deposited on the surface of the degradable film, and acrylic resin coated and photocured on the surface of the inorganic nano protective layer.
Wherein, the degradable material film is made of materials selected from PLA, PHA, PBAS, PPC, PVA, PHB, PBS, bioengineering plastics, and biological general plastics (polyolefin and polyvinyl chloride) starch base, etc.
Wherein, the degradable material film is selected from a single-layer or multi-layer mixed degradable material structure, and the thickness of the degradable material film ranges from 5 micrometers to 500 micrometers.
Wherein, the inorganic nano protective layer can be made of metal, metal oxide and inorganic nano material, and the thickness is 10-500 nm.
The inorganic nano protective layer can be a single nano material layer or a mixed layer of a plurality of nano materials.
Wherein, the thickness of the UV-cured acrylic resin layer is between 0.1 and 50 microns.
A preparation process of a degradable film with enhanced water-oxygen barrier performance by physical deposition comprises the following steps: the surface treatment is carried out on the ultrathin degradable film, the nano-scale compact barrier layer is deposited by a physical deposition technology, then the UV curing acrylic resin can be coated on the upper part, and the curing protection is finished after the UV irradiation, or the curing layer is not needed.
Wherein, the degradable material film surface treatment can be selected from methods of ozone, plasma, chemistry, corona and the like.
The physical deposition technology can be RF, DC or magnetron sputtering, vacuum evaporation, low-pressure evaporation, arc plasma plating, ion plating, molecular beam epitaxy and other methods.
The temperature of the degradable film can be kept within the range of room temperature to 80 ℃ by a physical deposition technology, and the film coating rate is 1-50 nm/min.
According to the design and the process, the coating and the structural scheme are simple, practical and efficient, and the method comprises the following steps:
in the first step, a thin film of material to be degraded is prepared and the surface may be cleaned. And putting the mixture into a vacuum drying oven to remove more water vapor and oxygen which are adsorbed, wherein the temperature is less than 60 ℃.
And secondly, putting the film into a pretreatment vacuum cavity to finish surface treatment. The plasma is transmitted into a plasma chamber to finish 50-100W oxygen or argon plasma treatment for 5-10 minutes, and the temperature is less than 60 ℃.
And thirdly, transferring the degradable film after the surface treatment into a physical deposition cavity (a vacuum RF sputtering cavity or a vacuum evaporation cavity).
And fourthly, sputtering or evaporating a 100-nanometer aluminum oxide film in the cavity. The temperature does not exceed 60 degrees celsius. RF sputtering (50-200W), sputtering inorganic nano-layer (ITO, SiO 2) of 5-500 nm. The temperature of the whole process is controlled below 60 ℃, and the sputtering process can not be sputtered at high temperature or too fast (the sputtering rate can not be too fast or too slow, and the depth and thickness of the nano-particles can be influenced).
And fifthly, introducing the sample into a nitrogen glove box with the temperature of 20 ℃ and the water and oxygen content of less than 1 ppm. The preparation is completed. Or coating a layer of UV-curable acrylic resin by a spin-on, dip-coating process, approximately 1-500 microns thick.
And sixthly, introducing the sample plated with the UV acrylic resin into a UV cavity, and carrying out UV irradiation curing for 3 minutes to finish the final shaping and protection of the sample.
Seventh, the degradable film obtained finally can reach the level of WVTR (water vapor permeability) lower than 10-3 g/m/day, even 10-4 g/m/day.
The basic principle of the invention is that dense nanometer metal, inorganic atoms and molecules are partially covered on the upper part of degradable organic molecules by utilizing a mild and precise physical deposition technology, and are partially filled among the molecules to form a dense nanometer barrier layer, and then the nanometer barrier layer and the degradable film can be protected and covered by a UV curing material. The plastic film prepared by the method not only has high water oxygen barrier property, but also greatly reduces the pressure and pollution to the environment. Meanwhile, the requirements of high performance of flexible electronic packaging and the requirements of environmental protection technology are met. The application range and long-term planning of the high water oxygen barrier film can be greatly improved. The high water oxygen barrier film can be applied to the substrate of flexible electronic products and can also be applied to the packaging process of the products. And the degradable film has the characteristics of environmental protection and health, and can be even applied to the fields with high sealing requirements of various medicines, organisms, preparations, foods and the like. The patent designs optimizes the preparation process and scheme of the degradable film in consideration of the stability in preparation of the nano layer. The problem of poor water oxygen barrier property of the original degradable material is solved from the design and preparation of the nano protective layer.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (10)
1. The degradable film with the water and oxygen barrier performance enhanced by physical deposition is characterized by comprising a degradable film, an inorganic nano protective layer physically deposited on the surface of the degradable film, and acrylic resin coated and photocured on the surface of the inorganic nano protective layer.
2. The degradable film with physical deposition enhancing water oxygen barrier property as claimed in claim 1, wherein the degradable material film is selected from PLA, PHA, PBAS, PPC, PVA, PHB, PBS, and bioengineering plastic, bio-general plastic (polyolefin and polyvinyl chloride) starch base, etc.
3. The physically deposited, water and oxygen barrier enhancing degradable film as claimed in claim 1, wherein the degradable material film is selected from a single layer or a multi-layer mixed degradable material structure, and the thickness of the degradable material film is in the range of 5 microns to 500 microns.
4. The physically degradable film with enhanced water and oxygen barrier properties as claimed in claim 1, wherein the inorganic nano protective layer is made of a material selected from the group consisting of metal, metal oxide and inorganic nano material and has a thickness of 10-500 nm.
5. The degradable film with physical deposition to enhance water and oxygen barrier property as claimed in claim 1, wherein the inorganic nano protective layer can be a single nano material layer or a mixed layer of multiple nano materials.
6. The physically degradable water and oxygen barrier film of claim 1 wherein said UV curable acrylic resin layer has a thickness of 0.1 to 50 microns.
7. A preparation process of a degradable film with enhanced water-oxygen barrier performance by physical deposition is characterized by comprising the following steps: the surface treatment is carried out on the ultrathin degradable film, the nano-scale compact barrier layer is deposited by a physical deposition technology, then the UV curing acrylic resin can be coated on the upper part, and the curing protection is finished after the UV irradiation, or the curing layer is not needed.
8. The process of claim 7, wherein the surface of the degradable material film is treated by ozone, plasma, chemical, corona or the like.
9. The process of claim 7, wherein the physical deposition technique is RF, DC or magnetron sputtering, vacuum evaporation, low pressure evaporation, arc plasma plating, ion plating, molecular beam epitaxy.
10. The process of claim 7, wherein the physical deposition technique is used to maintain the temperature of the degradable film within the range of room temperature to 80 ℃ and the coating rate is 1-50 nm/min.
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Cited By (1)
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