CN106929806B - High-barrier nano inorganic non-metallic film, preparation method thereof and vacuum winding coating equipment - Google Patents

High-barrier nano inorganic non-metallic film, preparation method thereof and vacuum winding coating equipment Download PDF

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CN106929806B
CN106929806B CN201610938315.XA CN201610938315A CN106929806B CN 106929806 B CN106929806 B CN 106929806B CN 201610938315 A CN201610938315 A CN 201610938315A CN 106929806 B CN106929806 B CN 106929806B
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潘振强
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Guangdong Zhenhua Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/081—Oxides of aluminium, magnesium or beryllium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/10—Glass or silica

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Abstract

The invention discloses a high-barrier nano inorganic non-metallic film, a preparation method thereof and vacuum winding coating equipment, comprising the following steps: placing a material to be evaporated in an electron gun annular crucible of an e-shaped electron gun group evaporation device; arranging the flexible base material at an unreeling device of a reeling transmission system, and completing film threading according to a reeling film-passing path; regulating and controlling the vacuum degree of a film coating chamber, starting a winding transmission system and an e-type electron gun group evaporation device, and evaporating a material to be evaporated at a high temperature to form an evaporation film on the surface of a flexible base material, wherein the e-type electron gun group is formed by combining at least two e-type electron guns; the power of the e-type electron gun is 1-10 kW. The evaporation process of the invention adopts the linear one-line or contraposition staggered arrangement mode of the e-shaped electron gun to emit the electron beam, thereby accelerating the evaporation rate, improving the production rate of the winding coating, reducing the production cost and more importantly obtaining the nano inorganic non-metallic oxide high-barrier film with excellent performance.

Description

High-barrier nano inorganic non-metallic film, preparation method thereof and vacuum winding coating equipment
Technical Field
The invention relates to the technical field of vacuum coating, in particular to a high-barrier nano inorganic non-metallic film, a preparation method thereof and vacuum winding coating equipment.
Background
Inorganic non-metal oxides such as silicon oxide (SiO)2) Alumina (Al)2O3) Titanium oxide (TiO)2) And the like, as a high-barrier material, has good barrier property, and particularly has excellent barrier property to oxygen and water vapor. The inorganic nonmetal nano barrier materials have more advantages, such as wider application range, suitability for refrigeration or direct heating, and better microwave permeability, and can be directly used for microwave heating; the inorganic non-metal barrier layer has excellent chemical resistance and can be used for packaging chemicals such as acid and alkali; the inorganic non-metal high-barrier film material has good transparency, the content is clear and visible, and the product display is more convenient; the high-barrier inorganic nano material can replace the conventional metal aluminum barrier layer packaging film material, reduces the use of metal materials, and hasEnvironment-friendly and pollution-free.
The preparation method of the vacuum winding coating film of the inorganic non-metal oxide generally comprises the following steps: plasma chemical vapor deposition winding coating, magnetron sputtering winding coating, high-temperature evaporation winding coating, atomic layer deposition winding coating and other winding coating. The plasma chemical vapor deposition process is to deposit silicon oxide barrier layer on the surface of plastic film with organic silane monomer (e.g. HMDSO) and oxygen in the assistance of plasma, and the side product produced during the reaction is exhausted via vacuum pump. The process has the advantages that the chemical vapor deposition method is adopted, so the silicon oxide barrier layer has better barrier property and strong adhesive force with the base material. And the intermediate frequency or radio frequency power supply is adopted in the process, the generated heat effect is low, and the influence of high temperature on the plastic substrate film is avoided. However, the process also has some defects, such as high investment, low production efficiency, and the speed of winding the coating film of about 200m/min, and in addition, the control in the process is particularly critical and has high requirements.
The magnetron sputtering winding coating mainly adopts Ar ions to bombard the surface of an inorganic non-metallic target material to generate an inorganic non-metallic material to deposit on the surface of a plastic film under the action of a magnetic field, and the process has the main defects of low sputtering rate, the winding coating speed of about 5m/min, easy electron enrichment on the surface of the target material in the process, target material surface poisoning, reduced sputtering strength and low production efficiency.
High temperature evaporation and winding of the coating with aluminum oxide (Al)2O3) For example, aluminum vapor is evaporated by feeding aluminum metal wire in different amounts, and the reactive deposition process is to place an oxygen gas nozzle in the evaporation area during the aluminum metal evaporation process, and finally deposit an aluminum oxide barrier layer on the surface of the plastic film substrate by plasma-assisted deposition. The winding coating speed in the reactive evaporation coating process is up to 500m/min, aluminum oxide is generated by adopting the thermal evaporation of the metal aluminum wire and the reaction of oxygen, the cost input of raw materials is low, the surface of the barrier film cannot present a light yellow appearance, the working efficiency is high, the industrial production is suitable, and the overall input is low compared with other process equipment. But instead of the other end of the tubeThe thermal evaporation reaction process is difficult to control, the barrier property of the alumina barrier layer is sensitive to the stretching deformation of the base material film due to the brittleness of the alumina barrier layer, and the barrier property of the product is in a medium level.
When the winding coating mode is used for preparing the high-barrier inorganic nonmetal oxide film, the defects of poor barrier property, uneven and non-compact film and the like exist. Therefore, a new winding coating mode is urgently needed at present, and the inorganic non-metal oxide nano film with better barrier property can be prepared.
Disclosure of Invention
The invention aims to provide a high-barrier nano inorganic non-metallic film, a preparation method thereof and vacuum winding coating equipment, wherein the high-barrier nano inorganic non-metallic oxide high-barrier film with excellent barrier property can be prepared only by adopting electron beam vacuum winding evaporation obtained by combining a plurality of e-type electron guns, the production rate of winding coating is improved, the economic benefit is increased, and the investment of production equipment cost is reduced.
In order to realize the aim, the invention provides a preparation method of a high-barrier nano inorganic non-metallic film, which comprises the following steps: placing a material to be evaporated in an electron gun annular crucible of an e-shaped electron gun group evaporation device; arranging the flexible base material at an unreeling device of a reeling transmission system, and completing film threading preparation according to a reeling film-moving path; regulating and controlling the vacuum degree of the film coating chamber, starting a winding transmission system and an e-type electron gun group evaporation device, and carrying out high-temperature evaporation on a material to be evaporated so as to form an evaporation film on the surface of the flexible substrate; wherein the e-type electron gun group is formed by combining at least two e-type electron guns; the power of the e-type electron gun is 1-10 kW; preferably 4 kW.
Furthermore, the e-type electron gun group is used by combining 3-5 e-type electron guns; preferably, 4 e-type electron guns are combined for use, and the 4 e-type electron guns are horizontally arranged and arranged in a linear row when combined; or mutually opposite and staggered to form parallelogram arrangement.
Further, the step of regulating and controlling the vacuum degree of the coating chamber comprises the following steps: miningPumping the vacuum degree of the coating chamber to a range required by the process evaporation by using a vacuum pump set; preferably to a vacuum plating of 3.0X 10-3Pa; then, auxiliary discharge gas is input into an input port at the upper end of the electronic gun crucible, and the working pressure in the coating chamber is adjusted to be 3.5-6.5 multiplied by 10-2Pa; preferably 5.0X 10-2Pa; the auxiliary discharge gas introduced during the evaporation of the electron gun is preferably oxygen; the temperature during evaporation is 1600-2100 ℃; when the material to be evaporated is silicon oxide, the evaporation temperature is preferably 1600 ℃; when the material to be deposited is alumina, the temperature to be deposited is preferably 2100 ℃.
Furthermore, the electron beam current of the e-type electron gun is 300-700 mA, and the voltage is-6.0 to-9.0 kV; preferably 400-600 mA, and the voltage is-7.0 to-8.0 kV; more preferably, the electron beam current is 500mA, and the voltage is-7.8 kV.
Further, after the film is evaporated by the electron beam, the method also comprises the step of bombarding the evaporated film by an ion source so as to improve the barrier property of the evaporated film; the number of the ion sources is the same as that of the e-type electron guns; the auxiliary discharge gas of the ion source is argon; preferably, the working voltage during ion source bombardment is 80-120V, and the working current is 3-6A; more preferably, the operating voltage is 100V and the operating current is 5A.
Further, the winding speed of the winding transmission system is 10-200 m/min; preferably 50-200 m/min; more preferably 100 m/min; preferably, the flexible substrate is a PET, PEN, or PA plastic film; the thickness of the flexible base material is 12-125 μm; preferably 50 to 90 μm.
According to another aspect of the invention, the high-barrier nano inorganic non-metallic film is prepared by any one of the methods.
According to another aspect of the present invention, there is also provided a vacuum winding coating apparatus for preparing a high-barrier nano inorganic non-metallic film, comprising:
the winding transmission device comprises an unwinding device and a winding device, and is used for unwinding the flexible substrate from the unwinding device and winding the flexible substrate on the winding device so that the flexible substrate is stretched on a surface with a refrigerating shaft and is exposed to an evaporation area of the evaporation source; the cooling device is arranged in the area to be evaporated, is provided with a refrigerating shaft and is used for cooling the evaporated film; the e-type electron gun group evaporation device is used as an evaporation source, is arranged below an evaporation area to be evaporated of the evaporation film transmission line, and is used for containing and heating a material to be evaporated to evaporate the material in the evaporation area and form an evaporation film on the surface of the flexible base material; the ion source auxiliary deposition device is arranged behind the cooling device and is used for bombarding the cooled evaporation coating film so as to improve the barrier property of the evaporation coating film; the evaporation device of the e-type electron gun assembly is formed by combining a plurality of electron gun crucibles.
Furthermore, the evaporation device of the e-type electron gun group consists of 3-5 e-type electron gun crucibles; more preferably 4 e-gun crucibles; 4 e-type electron gun crucibles are horizontally arranged and are arranged right below the evaporation area; the electron gun crucibles are arranged in a line or in a parallelogram shape by mutually opposite dislocation; evaporation angle range of each e-type electron gun
Figure GDA0002435652730000031
Is 30-45 degrees, preferably 35 degrees; the distance between adjacent e-type electron guns is 350mm
Further, an auxiliary discharge gas inlet is provided at the upper end of the electron gun crucible.
The invention has the beneficial effects that:
the invention adopts an electron beam evaporation winding evaporation process combined by a plurality of e-type electron guns, namely 4 e-type electron guns are horizontally placed under a cooling device to achieve maximum evaporation, the e-type electron guns are arranged in a linear line or a parallelogram for evaporation, the distance between adjacent e-type electron guns, the vertical distance between the e-type electron guns and a flexible substrate and the range of evaporation angles are controlled within a certain range, and simultaneously a winding transmission system is controlled to ensure that the flexible substrate to be evaporated is transmitted at a certain speed, and the parameter conditions during evaporation are limited within a certain range, thereby achieving the best evaporation and obtaining the nano inorganic non-metallic oxide high barrier film with excellent barrier property. The evaporation method adopts the e-type electron gun to emit the electron beams in a linear arrangement and combination mode, thereby not only accelerating the evaporation rate of the inorganic non-metallic material and improving the production rate of the winding coating, but also reducing the investment of the production equipment cost and increasing the economic benefit.
Drawings
FIG. 1 is a schematic view of a roll coating apparatus according to an exemplary embodiment of the present invention;
FIG. 2 is a schematic diagram of a structure of an evaporated film when 4 electron guns are horizontally arranged in an embodiment of the present invention;
FIG. 3 is a schematic diagram showing the arrangement of the vapor deposition materials in the electron gun crucible when depositing a thin film of an inorganic nonmetallic composite material in example 3 of the present invention.
Detailed Description
The technical solution of the present invention is explained in detail by the exemplary embodiments below. These examples should not be construed as limiting the scope of the invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise stated, the starting materials and reagents described in the examples are all commercially available products.
The electron gun adopts magnetic deflection type (e-shaped gun), because the electron beam winding path is approximate to e-shape, it can be divided into two kinds of 180 deg.C and 270 deg.C, its basic structure is divided into six portions of filament cathode, anode, focusing pole, permanent magnet, magnetic field coil and crucible, etc., the thermal electrons are released from high-heat cathode tungsten filament surface, and are accelerated by utilizing high-voltage electric field of cathode and front anode, and are collected into bundle by focusing pole and passed through central hole, and the magnetic field formed by magnetic field coil can be used for winding the moving direction of electron beam and making it be bent to the surface of material to be plated. The structure has an external magnetic field, secondary electrons generated by the crucible and the evaporation source material are deflected and guided away and absorbed under the action of the magnetic field, so that the influence caused by the secondary electrons can be reduced, the deflection of the electron beam is mainly controlled by the current of a magnetic field coil, the position of the X direction of the bombardment surface of the material of the electron beam can be moved by changing the size of the magnetic field, and if the magnetic field in the Y direction is added, planar pattern scanning in the XY directions can be simultaneously carried out, the hole digging phenomenon of the material is avoided, and the material can be uniformly consumed.
As shown in fig. 1 to 3, the present invention provides a winding coating apparatus for preparing a high-barrier nano inorganic non-metallic film. The winding coating equipment comprises a winding transmission system, an e-type electron gun group evaporation device 40, a cooling device 50 and an ion source auxiliary deposition device 60. The winding transmission device comprises an unwinding device 10, a winding device 20 and a transmission device for controlling, and the flexible substrate 30 is unwound and wound through the transmission device. One end of the flexible substrate 30 is set on the unwinding device 10 to start unwinding, and is transported by the guide roller 70 of the transmission device to extend on the surface of the cooling shaft of the cooling device 50 to be exposed in the evaporation area of the evaporation source, i.e. to enter the evaporation area above the e-type electron gun group evaporation device 40. And after the evaporation is finished, the vapor enters the winding device 20 for winding through a guide roller 70 of the transmission device.
The e-type electron gun group evaporation device 40 is arranged below the cooling device 50 of the film transmission line, and is used for containing and heating the material to be evaporated to evaporate in the evaporation area and forming an evaporation film layer on the surface of the flexible substrate 30. The e-gun set evaporation apparatus 40 may be formed by combining a plurality of electron gun crucibles. The electron gun crucible is horizontally placed and can be evaporated in a linear combination manner, for example, arranged in a row; or may be disposed in a mutually opposite offset manner, such as in a parallelogram manner.
The range of the evaporation angle can be adjusted according to the height of the vertical distance between the electron gun and the refrigeration shaft of the cooling device. To be provided with
Figure GDA0002435652730000051
The angle between the edge electron beam and the vertical line during evaporation is shown, and when the electron gun crucible is combined in a linear way, the evaporation angle range of each e-type electron gun
Figure GDA0002435652730000052
Is 30-45 degrees, preferably 35 degrees; and the distance between adjacent electron guns is 350 mm. The preferred evaporation device 40 is a 3-5 e-type electric deviceA sub-gun crucible; more preferably 4 e-gun crucibles.
The invention adopts four e-shaped electron guns which are horizontally arranged and arranged in a line, and the space between the adjacent electron guns and the evaporation angle range of the electron guns
Figure GDA0002435652730000053
Limited in a certain range, thereby having the advantages of large evaporation width, stable process and the like. The whole process is simple, the operation is convenient and safe, the winding speed during evaporation can be controlled by regulating the emission power of the e-type electron gun, the thickness of the nano inorganic non-metallic barrier layer on the surface of the flexible substrate 30 can be regulated, the barrier layer with better barrier performance requirements on oxygen and water vapor can be obtained, meanwhile, the continuous evaporation production is realized, and the e-type electron gun is started in the field of winding coating and coating processes of inorganic non-metallic oxides.
The invention also provides a preparation method of the high-barrier nano inorganic non-metallic film, which adopts the winding coating equipment for evaporation. The electron beam evaporation winding coating film is prepared by taking solid silicon oxide or aluminum oxide as an evaporation material, heating and evaporating the evaporation material into a gaseous state through an e-type electron gun, and then depositing the evaporated material on the surface of a flexible base material under the action of a cooling device to generate a transparent inorganic nano barrier layer. Compared with organic monomer materials, the raw materials evaporated by adopting the electron gun evaporation process are cheaper, the film coating efficiency is high, and the barrier layer has better barrier property.
Specifically, the winding evaporation process is realized by: first, e-type electron guns are arranged in a linear row or in a mutually opposite staggered arrangement according to requirements below a cooling device 50 of a film running route of a winding transmission system, and the same number of ion sources are arranged at the rear end of the film coating. After the preparation work of winding through the film is finished, inorganic non-metal materials to be evaporated, such as silicon oxide or aluminum oxide, or the two materials are added at intervals in the crucible of the electron gun, the vacuum chamber is closed, and the vacuum equipment is vacuumized. And starting a winding coating transmission system after the set process vacuum degree is reached, starting a power supply of the e-type electron gun after the winding speed of the flexible substrate reaches the set speed, opening a baffle above the e-type electron gun after the evaporation is stable, and performing evaporation of the nano inorganic non-metallic oxide film material on the flexible substrate wound above the e-type electron gun. And simultaneously starting an ion source at the rear end of the film-running path to bombard the evaporated film. Regulating and controlling the vacuum degree of the film coating chamber, starting the winding transmission system and the electron gun emission system, and performing high-temperature plating on the material to be evaporated so as to form an evaporated film layer on the surface of the flexible substrate.
The e-type electron gun group adopted by the invention can be formed by combining at least two e-type electron guns. Wherein, the power of the e-type electron gun is 1-10 kW, preferably 4 kW. According to the present invention, the e-type electron gun may be preferably used by combining 3 to 5 e-type electron guns. More preferably, 4 e-type electron guns are used in combination. When the 4 e-type electron guns are combined, the electron guns are horizontally arranged in a linear line or are mutually opposite and staggered to form parallelogram arrangement, for example, the 4 e-type electron guns form the parallelogram arrangement.
According to the invention, the electron beam current of the e-type electron gun is 300-700 mA, and the voltage is-6.0 to-9.0 kV. Preferably, the electron beam current of the e-type electron gun is 400-550 mA, and the voltage is-7.0 to-8.0 kV. More preferably, the electron beam current is 500mA, and the voltage is-7.8 kV. According to the invention, the electron beam current and the voltage of the electron gun are accurately controlled, so that the evaporation rate of the evaporation material is regulated and controlled, and the phenomenon that the evaporation rate of the material to be evaporated is too high, if the evaporation rate is too high, the particles of the evaporation film are larger, the evaporation film has more cracks, and the barrier property of the nano inorganic non-metal film is reduced is avoided. By regulating and controlling the electron beam current and the voltage, the evaporation power and the evaporation rate are kept within a certain range, so that the evaporation film with small particles, compact arrangement and small surface roughness is obtained, and the barrier property of the nano inorganic non-metal film is improved.
According to the invention, the step of regulating and controlling the vacuum degree of the coating chamber comprises the following steps: a vacuum pump set is adopted to pump the vacuum degree of the coating chamber to the range required by the process evaporation; preferably to a vacuum plating of 3.0X 10-3Pa. Then, auxiliary discharge gas is input into the upper end input port of the electronic gun crucible, and the work in the film coating chamber is regulatedThe air pressure is 3.5 to 6.5 x 10-2Pa; preferably 5.0X 10-2Pa. The auxiliary discharge gas introduced during electron gun vapor deposition is preferably oxygen. Because the electron beam energy is higher, if silicon oxide is directly evaporated, oxygen deficiency can be caused, the evaporated material can be oxidized by introducing oxygen, and the silicon oxide film is ensured to be deposited on the surface of the flexible substrate. The temperature during evaporation is 1600-2100 ℃. When the material to be evaporated is silicon oxide, the evaporation temperature is preferably 1600 ℃; when the material to be deposited is alumina, the temperature to be deposited is preferably 2100 ℃.
The evaporation radiation range of each e-type electron gun is about 300-350mm, and the combination of a plurality of e-type electron guns can meet the requirement of large-width film coating. The invention adopts the e-type electron gun to fully ionize the evaporated particles when in combined use, and the deposited nano film material has better quality, more compact film layer and better barrier effect.
In the preferred embodiment of the invention, the winding speed of the winding transmission system is 10-200 m/min; preferably 50-200 m/min; more preferably 100 m/min. The flexible substrate used in the invention can be PET, PEN or PA plastic film. The thickness of the flexible base material is 12-125 μm; preferably 50 to 90 μm.
According to the invention, after the thin film is evaporated, the method also comprises the step of bombarding the evaporated thin film by adopting an ion source. Preferably, the number of ion sources is the same as the number of e-guns. The auxiliary discharge gas of the ion source is argon. The invention uses ion source to bombard the evaporated oxide film, and the purpose is to bombard the film layer by high-energy ion source, so that the loose structure on the surface of the film layer can be tamped and compacted, and the large particles can be refined, and the roughness of the surface of the evaporated film can be reduced, thereby improving the surface compactness of the evaporated film and playing the role of improving the barrier property.
According to the invention, the working voltage during ion source bombardment is preferably 80-120V, and the working current is preferably 3-6A. More preferably, the operating voltage is 100V and the operating current is 5A.
Example 1
Alumina vapor deposition particles are uniformly added into an electron gun annular crucible, and the distance between adjacent electron guns during vapor deposition is adjusted to be 350 mm. And (3) placing the PET coiled material with the thickness of 12 mu m at an unreeling shaft of an unreeling device, and completing the film threading preparation work according to a winding film-passing path. And closing the film coating vacuum chamber to prepare for vacuumizing.
When the vacuum degree in the coating vacuum chamber reaches 5.0 multiplied by 10-3When the Pa background vacuum is adopted, oxygen is input through an oxygen input port at the upper end of the crucible of the electron gun, and the working air pressure of the coating is adjusted to 5.0 multiplied by 10-2Pa. And (3) opening an e-type electron gun to work, wherein the electron beam current is 550mA, the voltage is-8.0 kV, and the alumina vapor deposition particles are subjected to vapor deposition at the high temperature of about 2100 ℃. Starting a winding transmission system, and opening an upper baffle of the e-shaped electron gun after the evaporation is stable when the winding speed of the winding transmission system is set to be 100m/min, so that the evaporation angle range of the e-shaped electron gun is within
Figure GDA0002435652730000071
The evaporation plating of the nanometer alumina inorganic non-metallic material is carried out at 35 ℃.
After the evaporation is finished, the ion source sets the working current of 5A and the voltage of 100V at the rear end of the film transmission path, and bombards the evaporated silicon oxide film layer so as to improve the film quality. And (3) carrying out electron beam evaporation on the nano aluminum oxide inorganic nonmetal oxide of the PET film with the thickness of 12 microns according to the process parameters.
Example 2
Silicon oxide evaporation particles are uniformly added into an annular crucible of an electron gun, adjacent e-shaped electron guns are arranged at intervals in a staggered mode during evaporation, and the distance between the adjacent electron guns is 350 mm. And (3) placing the PET coiled material with the thickness of 12 mu m at an unreeling shaft of an unreeling device, and completing the film threading preparation work according to a winding film-passing path. The vacuum chamber is closed in preparation for evacuation.
The vacuum degree reaches 5.0 multiplied by 10-3When the Pa background vacuum is adopted, oxygen is input through an oxygen input port at the upper end of the crucible of the electron gun, and the working air pressure of the coating is adjusted to 5.0 multiplied by 10-2Pa. And opening an e-type electron gun to work, wherein the electron beam current is 500mA, the voltage is-7.8 kV, and the high-temperature evaporation at 1600 ℃ is carried out on the silicon oxide evaporation particles. The winding transmission system is started up and the winding transmission system is started up,when the winding speed of the winding transmission system is set to be 100m/min, the upper baffle of the e-shaped electron gun is opened after the evaporation is stable, so that the evaporation angle range of the e-shaped electron gun is in
Figure GDA0002435652730000081
The evaporation plating of the nanometer silicon oxide inorganic nonmetal high-barrier film is carried out at 35 ℃.
After the evaporation is finished, the ion source sets the working current of 5A at the rear end of the film transmission path, the voltage of 100V bombards the evaporated silicon oxide film layer, and the film quality is improved. And (3) carrying out electron beam evaporation on the nano silicon oxide inorganic nonmetal oxide of the PET film with the thickness of 12 microns according to the process parameters.
Example 3
As shown in fig. 3, electron gun crucible sets in which the particulate silica and alumina to be evaporated were placed were arranged in a line, and the distance between adjacent electron guns at the time of evaporation was adjusted to 350 mm. And (3) placing the PET coiled material with the thickness of 12 mu m at an unreeling position, and finishing the film threading preparation work according to a film reeling and running path. The vacuum chamber is closed in preparation for evacuation.
When the vacuum degree in the coating vacuum chamber reaches 5.0 multiplied by 10-3When the Pa background vacuum is adopted, oxygen is input through an oxygen input port at the upper end of the crucible of the electron gun, and the working air pressure of the coating is adjusted to 5.0 multiplied by 10-2Pa. And (3) opening the e-type electron gun to work, wherein the electron beam current of the e-type electron gun for evaporating and plating the aluminum oxide is 550mA, the voltage is-8.0 kV, and the electron beam current of the e-type electron gun for evaporating and plating the silicon oxide is 500mA, and the voltage is-7.8 kV. The silicon oxide vapor deposition particles were subjected to high-temperature vapor deposition at 1600 ℃ and the aluminum oxide vapor deposition particles were subjected to high-temperature vapor deposition at 2100 ℃.
Starting a winding transmission system, and opening an upper baffle of the e-shaped electron gun after the evaporation is stable when the winding speed of the winding transmission system is set to be 100m/min, so that the evaporation angle range of the e-shaped electron gun is within
Figure GDA0002435652730000082
Vapor deposition of nano-silica/alumina material was carried out at 35 ℃.
After the evaporation is finished, the ion source sets the working current of 5A and the voltage of 100V at the rear end of the film transmission path, and bombards the evaporated silicon oxide/aluminum oxide composite film layer so as to improve the film quality. And (3) carrying out electron beam evaporation on the nano silicon oxide inorganic nonmetal oxide of the PET film with the thickness of 12 microns according to the process parameters.
Comparative example 1
The preparation method is the same as that of the embodiment 3, except that in the comparative example 1, after the evaporation is finished, the silicon oxide/aluminum oxide composite film layer is not bombarded by an ion source at the rear end of the film transmission path so as to improve the film quality.
TABLE 1
Figure GDA0002435652730000091
Note: the oxygen transmission rate of a PET raw film having a thickness of 12 μm was 130cc/m2Day, water vapor transmission rate of 40g/m2Day; and (3) testing conditions are as follows: OTR: 25 ℃, RH 0%, WVTR: 38 ℃ and RH 90%.
From the results of examples 1-3 of the present invention, it can be seen that silicon oxide or aluminum oxide or silicon oxide/aluminum oxide vapor-deposited by the multi-group e-type electron beam winding vapor deposition apparatus of the present invention as the nano inorganic non-metal barrier film material all obtain vapor-deposited films with better barrier performance, and the products thereof meet the barrier performance requirements of conventional packaging. As is apparent from the data in table 1, the barrier layer performance obtained after evaporation of the single aluminum oxide material in example 1 and the single silicon oxide material in example 2 is not as good as that of the composite aluminum oxide/silicon oxide film in example 3, which indicates that the composite thin film layer with better oxygen and water vapor barrier performance can be prepared by the method.
Compared with the comparative example 1, in the embodiment 3, the ion source is adopted to bombard the evaporated composite film, particles evaporated by further ionization on the evaporation of silicon oxide/aluminum oxide can be bombarded and evaporated film layer can be tamped by bombarding the evaporated film layer through the bombardment of the ion source, so that the deposited film has better compactness, and the barrier property is further improved.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (24)

1. A preparation method of a high-barrier nano inorganic non-metallic film is characterized by comprising the following steps: placing a material to be evaporated in an electron gun annular crucible of an e-shaped electron gun group evaporation device (40); arranging a flexible substrate (30) at an unreeling device (10) of a reeling transmission system, and completing film threading preparation according to a reeling film-moving path; regulating and controlling the vacuum degree of the film coating chamber, starting a winding transmission system and an e-type electron gun group evaporation device (40), and carrying out high-temperature evaporation on a material to be evaporated so as to form an evaporation film on the surface of the flexible base material (30); wherein the e-type electron gun group is formed by combining at least two e-type electron guns; the power of the e-type electron gun is 1-10 kW;
after the film is evaporated by the electron beam, the method also comprises the step of bombarding the evaporated film by an ion source so as to improve the barrier property of the evaporated film; the number of the ion sources is the same as that of the e-type electron guns; the auxiliary discharge gas of the ion source is argon; the working voltage during ion source bombardment is 80-120V, and the working current is 3-6A; the device further comprises an ion source auxiliary deposition device which is arranged behind the cooling device and used for bombarding the cooled evaporation coating film so as to improve the barrier property of the evaporation coating film.
2. The method of claim 1, wherein the e-gun has a power of 4 kW.
3. The method according to claim 1, wherein the ion source bombardment is performed at an operating voltage of 100V and an operating current of 5A.
4. The method according to claim 1, wherein the e-type electron gun group is composed of 3 to 5 e-type electron guns.
5. The method according to claim 4, wherein the e-type electron gun assembly is composed of 4 e-type electron guns, and the 4 e-type electron guns are horizontally arranged in a linear row or in a parallelogram arrangement by being oppositely displaced.
6. The method according to claim 1, wherein the step of controlling the vacuum degree of the coating chamber comprises: a vacuum pump set is adopted to pump the vacuum degree of the coating chamber to the range required by the process evaporation; then, auxiliary discharge gas is input into an input port at the upper end of the electronic gun crucible, and the working pressure in the coating chamber is adjusted to be 3.5-6.5 multiplied by 10-2Pa; the auxiliary discharge gas introduced during the evaporation of the electron gun is oxygen; the temperature during evaporation is 1600-2100 ℃; when the evaporation material is silicon oxide, the evaporation temperature is 1600 ℃; when the material to be evaporated is alumina, the temperature to be evaporated is 2100 ℃.
7. The method according to claim 6, wherein the vacuum degree of the coating chamber is reduced to 3.0X 10-3Pa。
8. The production method according to claim 6, wherein the working pressure in the coating chamber is adjusted to 5.0X 10- 2Pa。
9. The method according to claim 1, wherein the e-type electron gun has a beam current of 300 to 700mA and a voltage of-6.0 to-9.0 kV.
10. The method as claimed in claim 9, wherein the e-type electron gun has a beam current of 400-600 mA and a voltage of-7.0-8.0 kV.
11. The method as claimed in claim 10, wherein the e-type electron gun has a beam current of 500mA and a voltage of-7.8 kV.
12. The method for preparing the rubber composition according to claim 1, wherein the winding speed of the winding transmission system is 10 to 200 m/min.
13. The method for preparing the rubber composition according to claim 12, wherein the winding speed of the winding transmission system is 50 to 200 m/min.
14. The method of claim 13, wherein the winding speed of the winding drive system is 100 m/min.
15. The method of manufacturing according to claim 1, wherein the flexible substrate (30) is a PET, PEN, or PA plastic film; the thickness of the flexible base material (30) is 12-125 μm.
16. The method of claim 15, wherein the flexible substrate (30) has a thickness of 50 to 90 μm.
17. A high-barrier nano inorganic non-metallic film, characterized in that it is prepared by the method of any one of claims 1 to 16.
18. A vacuum winding coating equipment is used for preparing high-barrier nano inorganic non-metallic films and is characterized by comprising the following components: the winding transmission device comprises an unwinding device (10) and a winding device (20), and is used for unwinding the flexible substrate (30) from the unwinding device (10), transmitting the flexible substrate through a guide roller (70) of the transmission device, and winding the flexible substrate onto the winding device (20) so that the flexible substrate stretches out on a surface with a refrigerating shaft and is exposed in an evaporation area of the evaporation source; a cooling device (50) which is arranged in the region to be evaporated and is provided with a refrigerating shaft and is used for cooling the evaporated film; an e-type electron gun group evaporation device (40) which is used as an evaporation source and is arranged below an evaporation area of an evaporation film transmission line and used for containing and heating a material to be evaporated to evaporate in the evaporation area and form an evaporation film on the surface of the flexible base material (30); the ion source auxiliary deposition device (60) is arranged behind the cooling device (50) and is used for bombarding the cooled evaporation coating film so as to improve the barrier property of the evaporation coating film; the e-type electron gun group evaporation device (40) is formed by combining a plurality of electron gun crucibles.
19. The vacuum roll coating apparatus according to claim 18, wherein the e-type electron gun set evaporation device (40) is composed of 3-5 e-type electron gun crucibles.
20. The vacuum roll coating apparatus according to claim 19, wherein the e-type electron gun set evaporation device (40) is composed of 4 e-type electron gun crucibles; and 4 e-type electron gun crucibles are horizontally arranged and are arranged right below the evaporation area.
21. The vacuum winding coating apparatus of claim 20, wherein the electron gun crucibles are arranged in a line or in a parallelogram shape with opposite dislocation; the evaporation angle range 2 theta of each e-shaped electron gun is 30-45 degrees.
22. The vacuum roll coating apparatus of claim 21, wherein each e-gun has a deposition angle 2 θ of 35 ℃.
23. The vacuum roll coating apparatus of claim 19, wherein the distance between adjacent e-guns is 350 mm.
24. The vacuum roll coating apparatus as claimed in claim 18, wherein an auxiliary discharge gas inlet port is provided at an upper end of the electron gun crucible.
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