Ultrahigh barrier film for industrial packaging and preparation method thereof
阅读说明：本技术 一种工业封装用超高阻隔薄膜及其制备方法 (Ultrahigh barrier film for industrial packaging and preparation method thereof ) 是由 秦丽丽 王小军 冯煜东 何丹 董茂进 王毅 王冠 蔡宇宏 夏成明 韩仙虎 于 2020-12-14 设计创作，主要内容包括：本发明公开了一种工业封装用超高阻隔薄膜及其制备方法,该薄膜以聚酯类柔性衬底为基底层,在基底层上沉积有若干层丙烯酸酯层、若干层金属纳米层和若干层陶瓷阻隔层；所述若干层丙烯酸酯层、若干层金属纳米层和若干层陶瓷阻隔层为交替层叠；所述丙烯酸酯层是通过湿法涂布制备而成；所述金属纳米层是通过磁控溅射制备而成；所述陶瓷阻隔层通过PECVD技术制备而成；本发明能够获得均匀、结合力强,且具有良好的防水、防氧化效果的薄膜。(The invention discloses an ultrahigh barrier film for industrial packaging and a preparation method thereof, wherein the film takes a polyester flexible substrate as a substrate layer, and a plurality of acrylate layers, a plurality of metal nano layers and a plurality of ceramic barrier layers are deposited on the substrate layer; the plurality of acrylate layers, the plurality of metal nano layers and the plurality of ceramic barrier layers are alternately laminated; the acrylate layer is prepared by wet coating; the metal nano layer is prepared by magnetron sputtering; the ceramic barrier layer is prepared by a PECVD technology; the invention can obtain a film which is uniform, has strong binding force and good waterproof and anti-oxidation effects.)
1. The ultrahigh-barrier film for industrial packaging is characterized in that a polyester flexible substrate is used as a substrate layer, and a plurality of acrylate layers, a plurality of metal nano layers and a plurality of ceramic barrier layers are deposited on the substrate layer; the plurality of acrylate layers, the plurality of metal nano layers and the plurality of ceramic barrier layers are alternately laminated; the acrylate layer is prepared by wet coating; the metal nano layer is prepared by magnetron sputtering; the ceramic barrier layer is prepared by a PECVD technology.
2. The ultra-high barrier film for industrial packaging of claim 1, wherein the film comprises a first ceramic barrier layer, a first metal nano-layer, a first acrylate layer, a second ceramic barrier layer, a second metal nano-layer and a second acrylate layer in sequence from a substrate layer to the top.
3. The ultra-high barrier film for industrial encapsulation according to claim 1 or 2, wherein the substrate layer is one of PET, PC, PMMA and PEN.
4. The ultra-high barrier film for industrial encapsulation according to claim 1 or 2, wherein the thickness of the base layer is between 6um and 125um, more preferably between 12um and 125um, and most preferably between 50um and 125 um.
5. The ultra-high barrier film for industrial encapsulation according to claim 1 or 2, wherein the thickness of the acrylate layer is between 1um and 3 um.
6. The ultra-high barrier film for industrial encapsulation according to claim 1 or 2, wherein the metal nanolayer metal material is one selected from Ag, Cu, Cr, Ti, NiCr.
7. The ultra-high barrier film for industrial packaging according to claim 1 or 2, wherein the thickness of the metal nano layer is 2-8 nm, preferably 2-6 nm.
8. The ultra-high barrier film for industrial packaging of claim 1 or 2, wherein the material of the ceramic barrier layer is selected from one of aluminum nitride, silicon oxide, silicon nitride and silicon oxynitride.
9. The ultra-high barrier film for industrial packaging as claimed in claim 1 or 2, wherein the thickness of the ceramic barrier layer is 10 to 65nm, preferably 15 to 60 nm.
10. A preparation method of an ultrahigh barrier film for industrial packaging is characterized by comprising the following steps:
step one, providing a base film;
secondly, forming a ceramic barrier layer on the base film by adopting a plasma chemical vapor deposition method;
thirdly, forming a metal nano layer on the ceramic barrier layer by adopting a magnetron sputtering method;
forming an acrylate layer on the metal nano layer by adopting a wet coating technology;
and step five, repeating the operation of the step two to the step four once on the acrylate layer, wherein the finally obtained film sequentially comprises a first ceramic barrier layer, a first metal nano layer, a first acrylate layer, a second ceramic barrier layer, a second metal nano layer and a second acrylate layer from the substrate layer to the top.
Technical Field
The invention belongs to the technical field of flexible substrate films and preparation methods thereof, and particularly relates to an ultrahigh barrier film for industrial packaging and a preparation method thereof.
Background
The quantum dot display and OLED are taken as representatives, and the requirements of high barrier capability of water vapor and oxygen are put forward to the industrial packaging film in the industries of related flexible display, flexible lighting and organic film batteries. For example, the quantum dot material of the core component of the OLED device is extremely sensitive to water and oxygen in the air, and once the water and the oxygen break through the protective film and enter the device, the device is blackened and the service life is terminated.
In a conventional OLED device, a rigid device such as glass is used as a substrate, and electrodes and organic functional layers are formed thereon. Packaging of such devices. A glass cover plate is added on the device and is bonded by epoxy resin. A cap-type package is formed between the glass and the cover plate to isolate the organic device from air, but over time the epoxy will gradually corrode and there is still a risk of air leaking into the internal device. Moreover, the encapsulation mode of the rigid substrate gradually fails to meet the development requirements of the flexible OLED display device.
Researchers have invented the deposition of inorganic thin films, typically aluminum oxide or silicon oxide, on flexible substrates followed by the deposition of a polymer layer. The flexible bottom-sinking film has certain flexibility, can be bent and deformed to a certain degree, is not easy to damage, and has application prospect compared with the traditional packaging mode. However, due to the microscopic particle growth mechanism, the single inorganic ceramic film inevitably has defects such as pinholes and the like, so that convenience is provided for a water and oxygen transmission path, and in order to obtain higher barrier performance, researchers generally have larger thickness of the deposited barrier layer, so that the film is brittle and has relatively low toughness, and the oxygen-proof and waterproof barrier performance of the product is easily reduced in the using process.
For defects generated by single-layer inorganic thin film deposition on a flexible substrate, researchers adopt an organic/inorganic/organic multilayer deposition technology, and utilize various modes such as magnetron sputtering deposition of an inorganic layer, electron beam evaporation deposition of an organic layer, or PECVD continuous deposition of organic/inorganic films, but the magnetron sputtering deposition mode is compact in film layer and good in binding force, but the speed is slow, the electron beam evaporation speed is high, but the film layer quality is poor. PECVD is used for depositing organic/inorganic substances, organic substances are micromolecular siloxane, and the capability of filling defects on the surface of an inorganic layer is limited.
According to the invention, the thickness of each layer is optimized through the staggered and laminated arrangement design of the metal nano layer and the ceramic layer, so that the defects of pinholes and the like of an inorganic layer by a wet coating process are increased on the premise that the barrier film has excellent water vapor and oxygen barrier capability, the defects are filled in by adopting a liquid leveling mode, the barrier film has more excellent barrier capability compared with a pure oxide or nitride, the flexibility and the reprocessing capability are greatly improved, a roll-to-roll deposition mode is adopted in the whole preparation process, and the barrier film is more suitable for industrial development of industrial packaging ultrahigh barrier films.
Disclosure of Invention
In view of the above, the invention provides an ultrahigh-barrier film for industrial packaging and a preparation method thereof, and the ultrahigh-barrier film is uniform and strong in bonding force and has good waterproof and anti-oxidation effects.
The technical scheme for realizing the invention is as follows:
an ultrahigh barrier film for industrial packaging takes a polyester flexible substrate as a substrate layer, and a plurality of acrylate layers, a plurality of metal nano layers and a plurality of ceramic barrier layers are deposited on the substrate layer; the plurality of acrylate layers, the plurality of metal nano layers and the plurality of ceramic barrier layers are alternately laminated; the acrylate layer is prepared by wet coating; the metal nano layer is prepared by magnetron sputtering; the ceramic barrier layer is prepared by a PECVD technology.
Further, the film is sequentially provided with a first ceramic barrier layer, a first metal nano-layer, a first acrylate layer, a second ceramic barrier layer, a second metal nano-layer and a second acrylate layer from the substrate layer to the top.
Further, the substrate layer is one of PET (polyethylene terephthalate), PC (polycarbonate), PMMA (polymethyl methacrylate) and PEN (polyethylene naphthalate).
Further, the thickness of the base layer is between 6um and 125um, more preferably between 12um and 125um, and most preferably between 50um and 125 um.
Furthermore, the thickness of the acrylate layer is between 1um and 3 um.
Further, the metal material of the metal nano layer is selected from one of Ag, Cu, Cr, Ti and NiCr, and the thickness of the metal nano layer is 2-8 nm, preferably 2-6 nm.
Furthermore, the material of the ceramic barrier layer is selected from one of aluminum nitride, silicon oxide, silicon nitride and silicon oxynitride, and the thickness of the ceramic barrier layer is 10-65 nm, preferably 15-60 nm.
A preparation method of an ultrahigh-barrier film for industrial packaging comprises the following steps:
step one, providing a base film;
secondly, forming a ceramic barrier layer on the base film by adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD) method;
thirdly, forming a metal nano layer on the ceramic barrier layer by adopting a magnetron sputtering method;
forming an acrylate layer on the metal nano layer by adopting a wet coating technology;
and step five, repeating the operation of the step two to the step four on the acrylate layer once, wherein the finally obtained film sequentially comprises a first ceramic barrier layer, a first metal nano layer, a first acrylate layer, a second ceramic barrier layer, a second metal nano layer and a second acrylate layer from the substrate layer to the top.
Has the advantages that:
the film is a multilayer composite film and is prepared by advanced technology, compared with the traditional barrier film, the preparation process is completely green, the operation is simple and easy, the raw material of the film can be quickly gasified, the prepared film is uniform and has strong bonding force, and the prepared film has good waterproof and anti-oxidation effects (WVTR)<4*10-5g/m2·day,OTR<3*10-4ml/m2Day), and the film has good light transmission and toughness, has excellent reprocessing performance, and is suitable for quantum dot display, OLED and other industrial packaging sensitive to water vapor and oxygen.
Drawings
FIG. 1 is a schematic diagram of the present invention.
Wherein, the 1-PET is a substrate; 2-a first SiOx layer; 3-a first NiCr nanolayer; 4-a first acrylate layer; 5-a second SiOx layer; 6-a second NiCr nanolayer; 7-second acrylate layer.
Detailed Description
Example 1
As shown in figure 1, PET with the thickness of 30 μm is taken as a substrate, plasma sputtering cleaning is carried out in a winding type PECVD (plasma enhanced chemical vapor deposition) chamber, hexamethyl siloxane and oxygen are introduced to prepare a SiOx/SiCxOy composite coating with the thickness of 30nm, then the SiOx/SiCxOy composite coating enters a magnetron sputtering vacuum chamber, a NiCr layer with the thickness of 3nm is prepared under the condition of double-target reactive sputtering of a Cr target and a Ni target, finally the NiCr layer enters a wet coating equipment micro-gravure coater to prepare an acrylate layer with the thickness of 1.5um, the second flow is repeated after curing, the PECVD system sequentially deposits the SiOx/SiCxOy composite coating with the thickness of 40nm, the magnetron sputtering vacuum system deposits the NiCr layer with the thickness of 2nm, the micro-gravure coater prepares an acrylate layer with the thickness of 2um<4×10-5g/m2·day,OTR<3×10-3cc/m2·day。
Example 2
Using 50 μm thick PC as substrate, performing plasma sputtering cleaning in winding PECVD, and introducing hexamethylSiloxane and oxygen are used for preparing SiOx/SiCxOy composite coating 50nm, then the SiOx/SiCxOy composite coating enters a magnetron sputtering vacuum chamber, a NiCr layer is prepared under the condition of double-target reactive sputtering of a Cr target and a Ni target by 3nm, finally the NiCr layer enters a micro-gravure coating machine of wet coating equipment to prepare an acrylate layer 2um, the second flow is repeated after curing, a PECVD system, a SiOx/SiCxOy composite coating 30nm, a magnetron sputtering vacuum system, a NiCr layer 2nm are deposited, the acrylate layer 3um is prepared by the micro-gravure coating machine, and the acrylate layer is wound and packaged after curing, so far, the preparation of the barrier film with excellent performance is finished, and the WVTR is<1×10-5g/m2·day,OTR<2×10-3cc/m2·day。
Example 3
Taking PEN with the thickness of 30 mu m as a substrate, carrying out plasma sputtering cleaning in a winding type PECVD (plasma enhanced chemical vapor deposition), introducing hexamethyl siloxane and oxygen to prepare a SiOx/SiCxOy composite coating with the thickness of 40nm, then entering a magnetron sputtering vacuum chamber, preparing a NiCr layer with the thickness of 2nm under the condition of Cr target and Ni target double-target reactive sputtering, finally entering a wet coating equipment micro-gravure coating machine to prepare an acrylate layer with the thickness of 2um, repeating the second flow after curing, sequentially adopting a PECVD system to deposit the SiOx/SiCxOy composite coating with the thickness of 40nm, using a magnetron sputtering vacuum system to deposit the NiCr layer with the thickness of 2nm, preparing an acrylate layer with the micro-gravure coating machine to prepare 3um, and carrying out winding and packaging after curing, thus finishing the preparation of the barrier film with excellent<2×10-6g/m2·day,OTR<4×10-4cc/m2·day。
Example 4
Using 125 mu m PET as a substrate, carrying out plasma sputtering cleaning in a winding type PECVD (plasma enhanced chemical vapor deposition) chamber, introducing hexamethyl siloxane and oxygen to prepare a SiOx/SiCxOy composite coating of 40nm, then entering a magnetron sputtering vacuum chamber, preparing a NiCr layer of 2nm under the condition of Cr target and Ni target double-target reactive sputtering, finally entering a wet coating equipment micro-gravure coater to prepare an acrylate layer of 2um, repeating the second flow after curing, sequentially adopting a PECVD system to deposit the SiOx/SiCxOy composite coating of 40nm, a magnetron sputtering vacuum system to deposit the NiCr layer of 2nm, preparing the acrylate layer of 3um by the micro-gravure coater, and carrying out winding and packaging after curing to finish the preparation of the barrier film with excellent performance, wherein WVTR is prepared<3×10-6g/m2·day,OTR<5×10-4cc/m2·day。
Example 5
Using PMMA with the thickness of 125 mu m as a substrate, carrying out plasma sputtering cleaning in a winding type PECVD (plasma enhanced chemical vapor deposition), introducing hexamethylsiloxane and oxygen to prepare a SiOx/SiCxOy composite coating with the thickness of 50nm, then entering a magnetron sputtering vacuum chamber, preparing a NiCr layer with the thickness of 3nm under the condition of Cr target and Ni target double-target reactive sputtering, finally entering a wet coating equipment micro-gravure coating machine to prepare an acrylate layer with the thickness of 3um, repeating the second process after curing, sequentially adopting a PECVD system to deposit the SiOx/SiCxOy composite coating with the thickness of 50nm, depositing a NiCr layer with the thickness of 1nm by using a magnetron sputtering vacuum system, preparing an acrylate layer with the micro-gravure coating machine, and carrying out coiling and packaging after curing to finish the preparation of the barrier film with excellent performance, wherein WVTR is<4×10-6g/m2·day,OTR<2×10-3cc/m2·day。
In summary, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.