CN117070925A - Diamond-like moisture-resistant coating on surface of flexible packaging material and preparation method and application thereof - Google Patents
Diamond-like moisture-resistant coating on surface of flexible packaging material and preparation method and application thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 95
- 239000011248 coating agent Substances 0.000 title claims abstract description 86
- 239000005021 flexible packaging material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000008021 deposition Effects 0.000 claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 40
- 230000004888 barrier function Effects 0.000 claims abstract description 24
- 238000004806 packaging method and process Methods 0.000 claims abstract description 7
- 238000000151 deposition Methods 0.000 claims description 47
- -1 ethylene, propylene Chemical group 0.000 claims description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 238000004140 cleaning Methods 0.000 claims description 19
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 19
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 18
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 14
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 3
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 3
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 3
- 239000004626 polylactic acid Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 31
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 238000005452 bending Methods 0.000 abstract description 2
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- 150000002500 ions Chemical class 0.000 description 53
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 239000011295 pitch Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
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- 238000001291 vacuum drying Methods 0.000 description 5
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- 230000002829 reductive effect Effects 0.000 description 3
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- 230000001070 adhesive effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004100 electronic packaging Methods 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
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- 230000007935 neutral effect Effects 0.000 description 2
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- 230000006978 adaptation Effects 0.000 description 1
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- 230000000844 anti-bacterial effect Effects 0.000 description 1
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- 238000005137 deposition process Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 238000002834 transmittance Methods 0.000 description 1
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Classifications
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
- C23C16/0245—Pretreatment of the material to be coated by cleaning or etching by etching with a plasma
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Inorganic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The invention provides a diamond-like moisture-resistant coating on the surface of a flexible packaging material, and a preparation method and application thereof, and relates to the technical field of moisture-resistant packaging protection. The invention takes a gaseous carbon source as working gas, and carries out anode layer linear ion source deposition on the surface of the flexible packaging material to form the diamond-like carbon moisture-resistant coating. The invention adopts the mode of anode layer linear ion source deposition to deposit the diamond-like moisture-resistant coating on the surface of the flexible packaging material, the deposition temperature is not more than 40 ℃, the diamond-like coating is deposited at near room temperature, the obtained diamond-like coating has good bonding force with the flexible material substrate, the surface of the coating does not have obvious crack after a plurality of bending cycles, and the bonding with the substrate is firm; the diamond-like coating has good compactness, and the diamond-like coating with high compactness is used as a physical barrier layer, so that the diffusion path of water molecules can be prolonged or blocked, and the moisture resistance of the flexible packaging material is greatly improved.
Description
Technical Field
The invention relates to the technical field of moisture-proof packaging protection, in particular to a diamond-like moisture-proof coating on the surface of a flexible packaging material, and a preparation method and application thereof.
Background
The Diamond-like carbon (DLC) coating is an inorganic material with excellent performances of good biocompatibility, high optical transparency, strong antibacterial property, high chemical stability and the like, so that the application field of the DLC coating is very wide, including aerospace, medical related instruments, electronic packaging and the like. However, in recent years, DLC has been studied mainly in friction lubrication and the like, and studies on moisture resistance thereof have been recently reported. The DLC coating prepared by common methods such as cathodic vacuum filtration arc, direct current magnetron sputtering, pulse laser deposition, microwave plasma chemical vapor deposition, electron cyclotron resonance chemical vapor deposition and the like has poorer adhesion, higher internal stress and easy crack generation, and has adverse effect on the moisture resistance performance, thereby limiting the application of the DLC coating in the field of moisture resistance package protection.
Disclosure of Invention
In view of the above, the invention aims to provide a diamond-like moisture-resistant coating on the surface of a flexible packaging material, and a preparation method and application thereof. The diamond-like moisture-resistant coating prepared on the surface of the flexible packaging material is firmly combined with the flexible packaging material, and has excellent moisture-resistant performance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a diamond-like moisture-resistant coating on the surface of a flexible packaging material, which comprises the following steps:
and (3) taking a gas carbon source as working gas, carrying out anode layer linear ion source deposition on the surface of the flexible packaging material to form the diamond-like carbon moisture-resistant coating, wherein the deposition temperature of the anode layer linear ion source deposition is not more than 40 ℃.
Preferably, the gaseous carbon source comprises one or more of methane, acetylene, propane, ethane, ethylene, propylene and butene.
Preferably, the flexible packaging material is polyethylene naphthalate, polyethylene terephthalate, polyurethane, polypropylene, polyethylene, polystyrene or polylactic acid.
Preferably, the conditions for the deposition of the anode layer linear ion source include: the target base distance is 2-30 cm, the vacuum degree is 0.1-5 Pa, the gas flow of the gas carbon source is 50-450 sccm, the ion source current is 0.3-5.0A, the ion source voltage is 40-800V, the deposition temperature is 19-36 ℃, and the deposition time is 5-90 min.
Preferably, before the anode layer linear ion source is deposited, glow discharge cleaning is further carried out on the surface of the flexible packaging material.
Preferably, the conditions of the glow discharge cleaning include: vacuum degree of 4.0X10 -3 ～6.0×10 -3 Pa; argon is introduced, and the air flow of the argon is 100-900 sccm; the bias voltage is-150 to-900V; the cleaning time is 2-30 min.
Preferably, the thickness of the diamond-like moisture-resistant coating is 100-900 nm.
The invention provides the diamond-like carbon moisture-resistant coating prepared by the preparation method.
Preferably, the diamond-like moisture barrier coating is a hydrogen-containing diamond-like coating.
The invention provides application of the diamond-like carbon moisture-resistant coating in moisture-resistant packaging protection.
The invention provides a preparation method of a diamond-like moisture-resistant coating on the surface of a flexible packaging material, which is characterized by comprising the following steps: and (3) taking a gas carbon source as working gas, and carrying out anode layer linear ion source deposition on the surface of the flexible packaging material to form the diamond-like carbon moisture-resistant coating. The invention adopts the mode of anode layer linear ion source deposition to deposit the diamond-like moisture-resistant coating on the surface of the flexible packaging material, the deposition temperature is not more than 40 ℃, the diamond-like coating is deposited at near room temperature, the obtained diamond-like coating has good bonding force with the flexible material substrate, the surface of the coating does not have obvious crack after a plurality of bending cycles, and the bonding with the substrate is firm; the obtained diamond-like coating has good compactness, and the diamond-like coating with high compactness is used as a physical barrier layer, so that the diffusion path of water molecules can be prolonged or blocked, and the moisture resistance of the flexible packaging material is greatly improved.
Further, the carbon source of the gas adopted by the invention is hydrocarbon gas, and a large amount of hydrocarbon neutral groups and H are generated after dissociation + 、C + And C x H y + The plasma is charged, so that the hydrogen-containing diamond-like carbon coating is formed, the compactness of the coating and the binding force with a substrate can be further enhanced, and the coating has high compactness and excellent binding force. In addition, the compactness, the binding force and the thickness of the diamond-like coating can be regulated and controlled by regulating the target base distance and the deposition time, so that the humidity resistance of the diamond-like coating can be regulated and controlled.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) contrast of cross-sections of diamond-like moisture barrier coatings prepared in examples 3 and 5, where a corresponds to example 3 and b corresponds to example 5 in FIG. 1;
FIG. 2 is a Raman spectrum of a diamond-like moisture barrier coating deposited by an anode layer linear ion source under different target pitches of examples 1 to 4, wherein a corresponds to the target pitch of example 1 of 7.6cm, b corresponds to the target pitch of example 2 of 10.6cm, c corresponds to the target pitch of example 3 of 13.6cm, and d corresponds to the target pitch of example 4 of 16.6cm;
FIG. 3 is a bar graph showing the results of the water vapor transmission rates of the diamond-like moisture barrier coatings prepared in examples 1 to 5, wherein a in FIG. 3 is a bar graph showing the water vapor transmission rates of the diamond-like moisture barrier coatings prepared in examples 1 to 4, and b is the water vapor transmission rate of the diamond-like coatings of examples 3 and 5 having different thicknesses when the target base distance is 13.6cm;
fig. 4 is an optical image and a surface SEM image of an anode layer linear ion source deposited diamond-like coating at a target distance of 13.6cm for example 3, where a corresponds to the planar state, b corresponds to the curved state, c corresponds to the surface SEM image before the curve, and d corresponds to the surface SEM image after the curve.
Detailed Description
The invention provides a preparation method of a diamond-like moisture-resistant coating on the surface of a flexible packaging material, which comprises the following steps:
and (3) taking a gas carbon source as working gas, and carrying out anode layer linear ion source deposition on the surface of the flexible packaging material to form the diamond-like carbon moisture-resistant coating.
In the present invention, the flexible packaging material is preferably polyethylene naphthalate, polyethylene terephthalate, polyurethane, polypropylene, polyethylene, polystyrene or polylactic acid.
In the present invention, the gaseous carbon source preferably includes one or more of methane, acetylene, propane, ethane, ethylene, propylene, and butene, more preferably acetylene.
The anode layer linear ion source is not particularly required, and anode layer linear ion sources well known to those skilled in the art can be adopted.
In the present invention, the conditions for the deposition of the anode layer linear ion source preferably include: the target base distance (the vertical distance between the linear ion source of the strip anode layer and the substrate center of the flexible packaging material) is 2-30 cm, preferably 7.6-16.6 cm, more preferably 10.6-13.6 cm; the vacuum degree is 0.1 to 5Pa, preferably 0.1 to 1Pa, more preferably 0.1 to 0.5Pa; gas and its preparation methodThe gas flow rate of the carbon source is 50 to 450sccm, preferably 100 to 250sccm, more preferably 160 to 180sccm; the ion source current is 0.3 to 5.0A, preferably 1 to 3A, more preferably 2.4 to 2.6A; the ion source voltage is 40 to 800V, preferably 100 to 500V, more preferably 360 to 363V; the deposition temperature is not more than 40 ℃, preferably 19-36 ℃, and the temperature change in the single deposition process is not more than 10 ℃; the deposition time is 5 to 90 minutes, preferably 15 to 45 minutes, more preferably 20 to 30 minutes. In the invention, the anode layer linear ion source has high gas ionization rate, low operating pressure, high deposition rate and large ion flux, and a large amount of hydrocarbon neutral groups and H are generated after dissociation of working gas in the process of the anode layer linear ion source deposition + 、C + 、C x H y + Under the action of Hall current and electromagnetic field, the energy particles are emitted to the substrate in the form of ion beams, and the surface diffusion, shallow injection and sputter etching actions are carried out, so that a diamond-like film with uniformity, compactness and good adhesive force is formed.
In the invention, the device for depositing the anode layer linear ion source (i.e. a film plating machine) comprises a cavity, and a rotating frame disk and an ion source which are arranged in the cavity, wherein the rotating frame disk and the ion source are vertically arranged in the cavity in a one-way manner; the rotating frame disc is provided with a substrate (namely flexible packaging material), and can apply bias voltage for realizing glow cleaning on the substrate by reasonably controlling the bias voltage in the film coating process (detailed description below); the ion source is used for coating.
In the present invention, before the deposition of the anode layer linear ion source, the method preferably further comprises glow discharge cleaning (that is, ion cleaning and etching) the surface of the flexible packaging material, specifically, after washing, ultrasonic cleaning and drying the surface of the flexible packaging material in sequence, placing the flexible packaging material into the cavity of the device for depositing the anode layer linear ion source, adjusting the target base distance to the above range, and then carrying out glow discharge cleaning.
In the invention, the water washing is preferably carried out by firstly washing with clear water and then washing with deionized water; the ultrasonic cleaning preferably comprises sequentially performing a first ultrasonic cleaning and a second ultrasonic cleaning; the first ultrasonic cleaning is preferably performed in petroleum ether, and the cleaning time is preferably 3min; the second ultrasonic cleaning is preferably performed in absolute ethyl alcohol, and the cleaning time is preferably 3min; the drying is preferably carried out in a vacuum oven.
In the present invention, the conditions for glow discharge cleaning preferably include: vacuum degree of 4.0X10 -3 ～6.0×10 - 3 Pa, preferably 4.5X10 -3 ～5×10 -3 Pa; argon is introduced, the air flow of the argon is 100-900 sccm, preferably 850-870 sccm, and the argon is preferably high-purity argon; the bias voltage is-150 to-900V, preferably-800 to-810V; the cleaning time is 2-30 min, preferably 12-15 min.
In the present invention, the thickness of the diamond-like moisture barrier coating is preferably 100 to 900nm, more preferably 500 to 900nm. The invention adopts a method of anode layer linear ion source deposition to deposit a compact DLC coating on the surface of a substrate; the anode layer linear ion source technology can provide energy required by high-energy ion beam and diamond-like coating deposition, so that the deposition can be carried out at near room temperature; the temperature is too high, the content of graphite phase in the deposited carbon film is high, the carbon film is loose, the moisture resistance performance is reduced, meanwhile, the thermal expansion coefficient is influenced by the temperature, the stress state of the carbon film is changed due to the too high temperature, and the carbon film may crack or peel. The diamond-like carbon moisture-resistant coating prepared by the invention has good compactness, good binding force with a flexible substrate and excellent moisture resistance. In addition, the invention can realize the controllability of the coating structure and thickness by adjusting the target base distance and the deposition time, thereby realizing the controllability of compactness and further realizing the control of moisture resistance.
The invention provides the diamond-like carbon moisture-resistant coating prepared by the preparation method. In the present invention, the diamond-like moisture barrier coating is preferably a hydrogen-containing diamond-like coating.
The invention provides application of the diamond-like carbon moisture-resistant coating in moisture-resistant packaging protection. The diamond-like carbon moisture-resistant coating provided by the invention has higher compactness, can form a physical barrier on the surface of the flexible packaging material to block the transmission of water vapor, improves the moisture-resistant performance of the flexible packaging material, is firmly combined with the flexible packaging material, has good adhesive force and allows certain deformation. Therefore, the diamond-like carbon moisture-resistant coating provided by the invention can be widely applied to the field of moisture-resistant packaging protection (such as food packaging, electronic packaging and the like).
For further explanation of the present invention, the following examples are provided to describe the diamond-like moisture barrier coating on the surface of the flexible packaging material, and the preparation method and application thereof in detail, but they should not be construed as limiting the scope of the invention.
Example 1
A linear ion source with a unidirectional vertical strip anode layer is adopted, the voltage of the ion source is 362V, and the current of the ion source is 2.5A. Self-cleaning polyethylene terephthalate (PET) is selected as a substrate for coating growth, wherein the polyethylene terephthalate is in a sheet shape of 13cm multiplied by 47 mu m; the flexible substrate is firstly cleaned by clean water and then cleaned by deionized water, then sequentially ultrasonic is carried out in petroleum ether and absolute ethyl alcohol for 3min, finally the flexible substrate is put into a vacuum drying oven for drying, the dried flexible substrate is put into a cavity, and the target base distance (the vertical distance between a linear ion source of a strip anode layer and the center of a substrate of a flexible packaging material) is adjusted to 7.6cm.
Before the experiment, the vacuum degree of the cavity is pumped to 5.0X10 -3 Pa, high-purity argon is introduced into 870sccm, and the substrate is cleaned by glow discharge for 15min under the partial pressure of-808V. Acetylene is introduced into the vacuum cavity, the flow rate of acetylene is 170sccm, and the vacuum degree is 4-4.2X10 -1 Pa, and the diamond-like carbon wet-resistant coating prepared by anode layer linear ion source deposition (the deposition temperature is 22-26 ℃ and the deposition time is 20 min) is marked as M1.
Example 2
A linear ion source with a unidirectional vertical strip anode layer is adopted, the voltage of the ion source is 362V, and the current of the ion source is 2.5A. Self-cleaning polyethylene terephthalate is selected as a substrate for coating growth, wherein the polyethylene terephthalate is in a sheet shape of 13cm multiplied by 47 mu m; the flexible substrate is firstly cleaned by clean water and then cleaned by deionized water, then sequentially ultrasonic is carried out on the flexible substrate in petroleum ether and absolute ethyl alcohol for 3min, finally the flexible substrate is put into a vacuum drying oven for drying, and the flexible substrate is put into a cavity after drying, and the target base distance is adjusted to be 10.6cm.
Before the experiment, the vacuum degree of the cavity is pumped to 5.0X10 -3 Pa, high-purity argon is introduced into 870sccm, and the substrate is cleaned by glow discharge for 15min under the partial pressure of-808V. Acetylene is introduced into the vacuum cavity, the flow rate of acetylene is 170sccm, and the vacuum degree is 4-4.2X10 -1 Pa, and performing linear ion source deposition (the deposition temperature is 22-26 ℃ and the deposition time is 30 min) on the anode layer to prepare the diamond-like carbon moisture-resistant coating which is denoted as M2.
Example 3
A linear ion source with a unidirectional vertical strip anode layer is adopted, the voltage of the ion source is 362V, and the current of the ion source is 2.5A. Self-cleaning polyethylene terephthalate is selected as a substrate for coating growth, wherein the polyethylene terephthalate is in a sheet shape of 13cm multiplied by 47 mu m; the flexible substrate is firstly cleaned by clean water and then cleaned by deionized water, then sequentially ultrasonic is carried out on the flexible substrate in petroleum ether and absolute ethyl alcohol for 3min, finally the flexible substrate is put into a vacuum drying oven for drying, and the flexible substrate is put into a cavity after drying, and the target base distance is adjusted to be 13.6cm.
Before the experiment, the vacuum degree of the cavity is pumped to 5.0X10 -3 Pa, high-purity argon is introduced into 870sccm, and the substrate is cleaned by glow discharge for 15min under the partial pressure of-808V. Acetylene is introduced into the vacuum cavity, the flow rate of acetylene is 170sccm, and the vacuum degree is 4-4.2X10 -1 Pa, and performing linear ion source deposition (the deposition temperature is 22-26 ℃ and the deposition time is 20 min) on the anode layer to prepare the diamond-like carbon moisture-resistant coating which is denoted as M3.
Example 4
A linear ion source with a unidirectional vertical strip anode layer is adopted, the voltage of the ion source is 362V, and the current of the ion source is 2.5A. Self-cleaning polyethylene terephthalate is selected as a substrate for coating growth, wherein the polyethylene terephthalate is in a sheet shape of 13cm multiplied by 47 mu m; the flexible substrate is firstly cleaned by clean water and then cleaned by deionized water, then sequentially ultrasonic is carried out on the flexible substrate in petroleum ether and absolute ethyl alcohol for 3min, finally the flexible substrate is put into a vacuum drying oven for drying, and the flexible substrate is put into a cavity after drying, and the target base distance is adjusted to be 16.6cm.
Before the experiment, the vacuum degree of the cavity is pumped to 5.0X10 -3 Pa, high-purity argon is introduced into 870sccm, and the substrate is cleaned by glow discharge for 15min under the partial pressure of-808V. Acetylene is introduced into the vacuum cavity, the flow rate of acetylene is 170sccm, and the vacuum degree is 4-4.2X10 -1 Pa, and performing linear ion source deposition (the deposition temperature is 22-26 ℃ and the deposition time is 30 min) on the anode layer to prepare the diamond-like carbon moisture-resistant coating which is denoted as M4.
Example 5
A linear ion source with a unidirectional vertical strip anode layer is adopted, the voltage of the ion source is 362V, and the current of the ion source is 2.5A. Self-cleaning polyethylene terephthalate is selected as a substrate for coating growth, wherein the polyethylene terephthalate is in a sheet shape of 13cm multiplied by 47 mu m; the flexible substrate is firstly cleaned by clean water and then cleaned by deionized water, then sequentially ultrasonic is carried out on the flexible substrate in petroleum ether and absolute ethyl alcohol for 3min, finally the flexible substrate is put into a vacuum drying oven for drying, and the flexible substrate is put into a cavity after drying, and the target base distance is adjusted to be 13.6cm.
Before the experiment, the vacuum degree of the cavity is pumped to 5.0X10 -3 Pa, high-purity argon is introduced into 870sccm, and the substrate is cleaned by glow discharge for 15min under the partial pressure of-808V. Acetylene is introduced into the vacuum cavity, the flow rate of acetylene is 170sccm, and the vacuum degree is 4-4.2X10 -1 Pa, and performing linear ion source deposition (the deposition temperature is 22-26 ℃ and the deposition time is 30 min) on the anode layer to prepare the diamond-like carbon moisture-resistant coating which is denoted as M5.
FIG. 1 is a Scanning Electron Microscope (SEM) contrast of cross-section of the diamond-like moisture barrier coating prepared in example 3 and example 5, and FIG. 1 a corresponds to example 3 and b corresponds to example 5. As can be seen from fig. 1, at a target base distance of 13.6cm, example 5 increased the coating thickness relative to example 3, but was still in the nanometer range.
FIG. 2 is a Raman spectrum of a diamond-like moisture barrier coating deposited from an anode layer linear ion source at different target pitches of examples 1-4, wherein a corresponds to example 1 target pitch of 7.6cm, b corresponds to example 2 target pitch of 10.6cm, c corresponds to example 3 target pitch of 13.6cm, and d corresponds to example 4 target pitch of 16.6cm. As can be seen from FIG. 2, example 3When the target base distance is 13.6cm, the prepared diamond-like carbon moisture-resistant coating I D /I G The minimum value of (2) indicates that the sp3 content of the coating is the greatest, the diamond phase content is high, and the compactness is good compared with other examples.
The diamond-like moisture barrier coatings prepared in examples 1 to 5 were tested for water vapor transmission rate at 25℃and relative humidity of 80%. Fig. 3 is a bar graph showing the results of the water vapor transmission rates of the diamond-like moisture barrier coatings prepared in examples 1 to 5, and fig. 3a is a bar graph showing the water vapor transmission rates of the diamond-like moisture barrier coatings prepared in examples 1 to 4, and b is the water vapor transmission rates of the diamond-like coatings of different thicknesses in examples 3 and 5 when the target base distance is 13.6cm. Test results shown in fig. 3 a: the water vapor transmission rate of the virgin polyethylene terephthalate (PET) is about 3.5 g/(m) 2 24 h), the water vapor transmission rate shows a change of decreasing and then increasing with increasing target base distance, and at 13.6cm, the water vapor transmission rate is minimum, 19 times lower than that of polyethylene terephthalate, and the coating shows good moisture-blocking effect. According to the test results, the diamond-like carbon coating is equivalent to a barrier, prevents the entry and diffusion of water vapor, and further reduces the water vapor transmission rate of the diamond-like carbon/polyethylene terephthalate composite material. The results shown in fig. 3 b demonstrate that thicker coatings have better moisture barrier properties than the original polyethylene terephthalate, and that the 793nm thick diamond-like coating of example 5 has a water vapor transmission rate reduced by a factor of about 30 and a factor of about 1.6 compared to the 512nm thick diamond-like coating of example 3.
Fig. 4 is an optical image and a surface SEM image of an anode layer linear ion source deposited diamond-like coating at a target distance of 13.6cm for example 3, where a corresponds to the planar state, b corresponds to the curved state, c corresponds to the surface SEM image before the curve, d corresponds to the surface SEM image after the curve, and d is a surface image within the selected b-box. The results of FIG. 4 show that the diamond-like coating was still intact after being bent 2160 times at a bend radius of 0.5cm, and the surface did not develop significant cracks, indicating that the coating was firmly bonded to the substrate.
According to the embodiment, the diamond-like carbon moisture-resistant coating is prepared by the anode layer linear ion source deposition, so that the diffusion path of water molecules can be prolonged or blocked, the water vapor transmittance is effectively reduced, the moisture-resistant performance is improved, and the diamond-like carbon moisture-resistant coating can be firmly combined with a flexible packaging material.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the diamond-like moisture-resistant coating on the surface of the flexible packaging material is characterized by comprising the following steps of:
and (3) taking a gas carbon source as working gas, carrying out anode layer linear ion source deposition on the surface of the flexible packaging material to form the diamond-like carbon moisture-resistant coating, wherein the deposition temperature of the anode layer linear ion source deposition is not more than 40 ℃.
2. The method of claim 1, wherein the gaseous carbon source comprises one or more of methane, acetylene, propane, ethane, ethylene, propylene, and butene.
3. The method of claim 1, wherein the flexible packaging material is polyethylene naphthalate, polyethylene terephthalate, polyurethane, polypropylene, polyethylene, polystyrene, or polylactic acid.
4. The method of claim 1, wherein the conditions for the deposition of the anode layer linear ion source include: the target base distance is 2-30 cm, the vacuum degree is 0.1-5 Pa, the gas flow of the gas carbon source is 50-450 sccm, the ion source current is 0.3-5.0A, the ion source voltage is 40-800V, the deposition temperature is 19-36 ℃, and the deposition time is 5-90 min.
5. The method of claim 1 or 4, further comprising glow discharge cleaning the surface of the flexible packaging material prior to depositing the anode layer linear ion source.
6. The method of claim 5, wherein the glow discharge cleaning conditions comprise: vacuum degree of 4.0X10 -3 ～6.0×10 -3 Pa; argon is introduced, and the air flow of the argon is 100-900 sccm; the bias voltage is-150 to-900V; the cleaning time is 2-30 min.
7. The method of claim 1, wherein the diamond-like moisture barrier coating has a thickness of 100 to 900nm.
8. A diamond-like moisture barrier coating prepared by the method of any one of claims 1 to 7.
9. The diamond-like moisture barrier coating of claim 8, wherein the diamond-like moisture barrier coating is a hydrogen-containing diamond-like coating.
10. Use of a diamond-like moisture barrier coating as claimed in claim 8 or 9 in moisture barrier packaging protection.
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