CN111073016A

CN111073016A - Degradable film with enhanced water-oxygen barrier performance by chemical vapor deposition

Info

Publication number: CN111073016A
Application number: CN201911337533.8A
Authority: CN
Inventors: 林群
Original assignee: Nanjing Fushibao New Material Co ltd
Current assignee: Nanjing Fushibao New Material Co ltd
Priority date: 2019-12-23
Filing date: 2019-12-23
Publication date: 2020-04-28

Abstract

The invention discloses a preparation process of degradable film with high water oxygen barrier property by chemical vapor deposition, which can meet the requirement of large-area preparation of high-performance water oxygen barrier films of various ultrathin and flexible electronic devices, medical treatment, biology and the like, and particularly realizes the rapid preparation and integration of large-area nano film layers and degradable films by low-pressure/normal-pressure chemical vapor deposition, thereby realizing the function of improving the water oxygen barrier of the degradable films.

Description

Degradable film with enhanced water-oxygen barrier performance by chemical vapor deposition

Technical Field

The invention belongs to the field of chemical vapor deposition, and particularly relates to a degradable film with enhanced water and oxygen barrier performance under low pressure or normal pressure.

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 provide a novel high-water-oxygen-barrier degradable packaging film which is prepared by preparing a high-density nano layer (or a UV acrylic resin protective layer thereon) on a degradable film through low-cost and high-efficiency low-pressure/normal-pressure chemical vapor deposition. Thereby overcoming the above-mentioned drawbacks of the prior art.

In order to achieve the above object, the present invention provides a degradable film with enhanced water-oxygen barrier properties by chemical vapor deposition, comprising a degradable film and a dense oxide layer deposited on the degradable film by chemical vapor deposition.

The method is a film preparation process which is established on the high-efficiency low-pressure/normal-pressure chemical vapor deposition technology and combines a nano barrier layer with a degradable film (or the advantages of a UV-curable acrylic resin), a single-layer or multi-layer nano compact layer is prepared by utilizing precursor molecules and reaction gas molecules in a cavity in the low-pressure/normal-pressure chemical vapor deposition technology, and the water and oxygen barrier property of the original degradable film or material is efficiently improved by 3-6 orders of magnitude, so that the disadvantages and shortcomings of the degradable film in the aspect of the water and oxygen barrier property are greatly improved. This technique allows the degradable film to also possess similar water oxygen barrier properties to conventional, commercialized plastic films. Due to the high water oxygen barrier performance, the degradable film and the plastic have the prospect and potential of application in the field of flexible high encapsulation. Although the traditional and existing plastic and polymer films have mature technical schemes and higher water-oxygen barrier performance, the development of the traditional and existing plastic and polymer films in the fields of flexibility and film electronics is also restricted by the original unexplained environmental-friendly garbage problem. It causes social and industrial problems such as environmental, recycling, abandonment, disposal, etc: for example: 1. the flexible electronic product can generate new electronic garbage and plastic garbage at the same time, and 2. different plastics and electronic products are difficult to uniformly recover and separate. 3 adding new problems and costs to the existing waste recovery and classification. The flexible plastic/polymer brings the advantages of the flexible plastic/polymer into the electronic industry, and brings environmental problems of environmental protection, recycling and the like into the electronic industry. 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 a new degradable film which can be encapsulated and has high water oxygen barrier is developed, the damage of the product to the environment and the society can be reduced from the beginning. The method effectively deposits a compact nano layer on the degradable film in a large area at low cost by utilizing a low-pressure/normal-pressure chemical vapor 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. Because of the low pressure/atmospheric pressure chemical vapor deposition techniques employed, it is also possible to use in combination with UV-curable acrylics: 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. Due to the adoption of low pressure/normal pressure chemical vapor deposition, the preparation of the high-efficiency compact nano layer is greatly promoted, for example, the preparation of large-area roll to roll can be realized, the equipment cost is low, the production cost is low, the rapid preparation is realized, and the like. 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 by using a low-cost and high-efficiency low-pressure/normal-pressure chemical vapor deposition preparation technology. 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 problem of a plurality of plastic films used in the packaging process of the current flexible electronic device to harm the environment and be undegradable is solved, and the plastic packaging film is a novel plastic pollution source. Meanwhile, the problems of equipment cost, preparation cost, coating efficiency and the like of a plurality of nano compact preparation schemes cause that the yield and the cost of the preparation are not satisfactory. The basic principle of the invention is to prepare nano-scale inorganic atoms and molecules by cheap and simple molecular chemical reaction by using low-cost and large-area preparation low-pressure/normal-pressure chemical vapor deposition. The nano molecules during and after the reaction are partially covered on the degradable organic molecules, and are partially filled among the molecules to form a compact nano barrier layer, and the subsequent nano barrier layer and the degradable film can be protected and covered by the UV curing material. In addition, because the low pressure/normal pressure chemical vapor deposition technology is a nano molecular reaction completed on the surface of the degradable film, a compact nano layer generated by the reaction can be firmly connected on the molecules of the degradable 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. Compared with other nanometer compact layer deposition technologies, the low-pressure/normal-pressure chemical vapor deposition is more economical, and the cost and the yield are more advantageous. 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, an acrylic resin layer is coated and photocured on the dense oxide layer.

Preferably, in the above technical solution, the degradable material film is selected from PLA, PHA, PBAS, PPC, PVA, PHB, PBS, and starch-based bioengineering plastics, and bio-versatile plastics (polyolefins and polyvinyl chloride).

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 material of the dense nano layer is selected from metals and inorganic oxides, and may be a single nano material layer or a mixed layer of multiple nano materials.

A preparation process of a degradable film with enhanced water and oxygen barrier performance by chemical vapor deposition comprises the following steps: surface treatment is carried out on the ultrathin degradable film, and then a low-pressure/normal-pressure chemical vapor deposition nanometer-level compact barrier layer is carried out.

Preferably, in the above technical solution, the surface treatment of the degradable material film can be selected from one of ozone, plasma, chemical and corona

Preferably, in the above technical solution, the chemical vapor deposition technique may be performed by injecting the precursor and the oxidizing gas into the chamber respectively in a low pressure or normal pressure environment.

Preferably, in the above technical scheme, the chemical vapor deposition technology has a low pressure of 1-104 pascal and a normal pressure of one atmosphere.

Preferably, in the above technical scheme, the temperature of the degradable film can be kept within a range from room temperature to 80 ℃, the degradable film cannot be heated to exceed the degradation temperature of the film, and the plating rate is 1-50 nm/min by using the chemical vapor deposition technology.

Preferably, in the above technical solution, the precursor may be selected from metal halides, metal hydrides, organic compounds, and the like.

Preferably, in the above technical solution, the oxidizing gas may be selected from oxygen, water vapor, ozone, oxygen plasma, high oxidizing gas, and the like.

Preferably, in the technical scheme, the upper part of the compact barrier layer is coated with UV-cured acrylic resin, and the curing protection is completed after UV illumination.

Preferably, in the above technical solution, the thickness of the UV-curable acrylic resin layer is between 0.1 and 50 μm.

The mild low-pressure/normal-pressure chemical vapor deposition scheme near room temperature can effectively deposit a compact nano layer in the degradable film, and simultaneously effectively utilize the precursor and the reaction molecules to fill the gaps between the molecules in the deposition process, so as to jointly achieve the purpose of blocking the water and oxygen molecules from penetrating through the film. Compared with the published technology, the technology has the advantages that the compactness, the uniformity and the reliability of the nano layer are greatly improved in large-area and low-cost preparation of the nano compact layer, 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 can control the reaction speed during the reaction of nano molecules, ensure the reaction molecules, and gas can uniformly cover the upper surface and the middle of the degradable material molecules.

D. The dense nano-layer generated by the chemical reaction in the gas phase chemical precipitation is metal oxide, inorganic oxide and the like with the atomic or molecular diameter smaller than 1 nanometer, so that water and oxygen molecules can be effectively blocked.

E. The final nanolayer may or may not be protected by a UV curable layer. .

Description of the drawings:

FIG. 1 is a schematic flow diagram of the present invention;

fig. 2 is a schematic view of the layered structure of the present invention.

In the figure: 1. a degradable film. 2. The surface of the degradable film is prepared into a compact nano layer in a low pressure/normal pressure chemical vapor deposition cavity. 3. And preparing the finished inorganic nano protective layer. 4. Covering with a light-curing acrylic resin. 5. A metal halide precursor is injected into the chamber. 6. The reactive oxidizing gas is injected into the chamber.

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 chemical vapor deposition degradable film for enhancing water oxygen barrier performance comprises a degradable film and a compact oxide layer deposited on the degradable film through chemical vapor deposition.

Optionally, an acrylic resin layer is coated and photocured on the dense oxide layer.

Optionally, the degradable material film is selected from PLA, PHA, PBAS, PPC, PVA, PHB, PBS, and starch-based bioengineering plastics, and bio-versatile plastics (polyolefins and polyvinyl chloride).

Optionally, 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.

Optionally, the dense nano layer is made of a material selected from metals and inorganic oxides, and may be a single nano material layer or a mixed layer of multiple nano materials.

Optionally, the surface of the degradable material film is treated by a method selected from ozone, plasma, chemistry and corona

Optionally, the chemical vapor deposition technique may be performed by injecting the precursor and the oxidizing gas into the chamber under low pressure or normal pressure.

Optionally, the chemical vapor deposition technique has a low pressure of 1-104 pascal and a normal pressure of one atmosphere.

Optionally, by using the chemical vapor deposition technology, the temperature of the degradable film can be kept within the range of room temperature to 80 ℃, the degradable film cannot be heated to exceed the degradation temperature of the film, and the film plating rate is 1-50 nm/min.

Alternatively, the precursor may be a material selected from metal halides, metal hydrides, organic compounds, and the like.

Alternatively, the oxidizing gas may be selected from oxygen, water vapor, ozone, oxygen plasma, highly oxidizing gases, and the like.

Optionally, the upper part of the dense barrier layer is coated with UV (ultraviolet) curing acrylic resin, and curing protection is completed after UV illumination.

Optionally, the UV-curable acrylic resin layer has a thickness of between 0.1 and 50 microns.

According to the design and the process of the invention, the nano-layer coating and the structural scheme are simple, large-area and low-cost, and the following steps are adopted:

in a first step, a thin film 1 of a material to be degraded is prepared, and the surface can be cleaned. And putting the film into a chemical vapor deposition cavity to extract vacuum, and removing more water vapor and oxygen which are adsorbed, wherein the temperature is less than 60 ℃.

And secondly, filling nitrogen and keeping the air pressure at 1 kilopascal.

Thirdly, keeping the low pressure at 1-10⁴Pascal, repeated and sequential injection of reactive metal halides and pure oxygen using a pipelineSo as to achieve the repeated nano-molecular reaction and deposition. The temperature of the whole process is controlled below 60 ℃, and meanwhile, the sputtering process can not be sputtered at high temperature or too fast (the reaction precursor and the oxidizing gas can not be repeated too fast, so that the reaction is insufficient, and the quality of the nano compact layer is reduced).

And fourthly, vacuumizing and injecting oxygen to react with the precursor on the surface of the film to form a nano SiO2 layer.

And fifthly, repeating the steps 3 and 4 repeatedly to achieve the purpose of multilayer film coating.

And sixthly, transferring the sample subjected to the nano coating into a glove box, and spin-coating a UV acrylic resin film with the thickness of 30-50 microns.

And seventhly, 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.

And eighth step, the degradable film obtained finally can reach the level that WVTR (water vapor permeability) is lower than 10-3 g.

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

1. The chemical vapor deposition degradable film for enhancing the water and oxygen barrier performance is characterized in that: comprising a degradable film and a dense oxide layer deposited on the degradable film by chemical vapor deposition.

2. The chemical vapor deposition degradable film for enhancing water oxygen barrier properties of claim 1 wherein: and coating and photocuring an acrylic resin layer on the dense oxide layer.

3. The chemical vapor deposition degradable film for enhancing water oxygen barrier properties of claim 1 wherein: the degradable material film is selected from PLA, PHA, PBAS, PPC, PVA, PHB, PBS, bioengineering plastic, biological general plastic starch base, or 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.

4. The chemical vapor deposition degradable film for enhancing water oxygen barrier properties of claim 1 wherein: the compact oxide layer is made of metal and inorganic oxide, and can be a single nanometer material layer or a mixed layer of multiple nanometer materials.

5. A preparation process of a degradable film with enhanced water and oxygen barrier performance by chemical vapor deposition is characterized by comprising the following steps: surface treatment is carried out on the ultrathin degradable film, and then a low-pressure/normal-pressure chemical vapor deposition nanometer-level compact barrier layer is carried out.

6. The process for preparing degradable film with enhanced water-oxygen barrier property by chemical vapor deposition according to claim 5, wherein the surface treatment of the degradable material film is selected from ozone, plasma, chemical, corona, and the method for preparing degradable film with enhanced water-oxygen barrier property by chemical vapor deposition according to claim 5, wherein the chemical vapor deposition technique is performed by injecting precursor and oxidizing gas into the chamber under low pressure and/or normal pressure, wherein the low pressure is 1-10⁴Pascal, normal pressure is one atmosphere.

7. The process of claim 6, wherein the chemical vapor deposition can maintain the temperature of the degradable film within the range of room temperature to 80 ℃ and can not be heated to exceed the degradation temperature of the film, and the coating rate is 1-50 nm/min.

8. The process of claim 7, wherein the precursor is selected from one of metal halides, metal hydrides and organic compounds; the oxidizing gas may be one selected from oxygen, water vapor, ozone, oxygen plasma, and high oxidizing gas.

9. The process for preparing a degradable film with enhanced water and oxygen barrier properties by chemical vapor deposition according to claim 6, wherein the upper part of the dense barrier layer is coated with UV-curable acrylic resin, and the curing protection is completed after UV illumination; a UV-cured acrylic resin layer having a thickness of between 0.1 and 50 microns.