WO2023197812A1 - 一种dlc涂层、其制备方法及设备及复合涂层、涂覆制品 - Google Patents

一种dlc涂层、其制备方法及设备及复合涂层、涂覆制品 Download PDF

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Publication number
WO2023197812A1
WO2023197812A1 PCT/CN2023/081532 CN2023081532W WO2023197812A1 WO 2023197812 A1 WO2023197812 A1 WO 2023197812A1 CN 2023081532 W CN2023081532 W CN 2023081532W WO 2023197812 A1 WO2023197812 A1 WO 2023197812A1
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monomer
coating
dlc coating
dlc
silane
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PCT/CN2023/081532
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English (en)
French (fr)
Inventor
宗坚
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Jiangsu Favored Nanotechnology Co Ltd
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Jiangsu Favored Nanotechnology Co Ltd
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Priority to JP2024560615A priority Critical patent/JP2025512104A/ja
Priority to EP23787460.7A priority patent/EP4509639A4/en
Priority to US18/856,725 priority patent/US20250243579A1/en
Publication of WO2023197812A1 publication Critical patent/WO2023197812A1/zh
Anticipated expiration legal-status Critical
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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/62—Plasma-deposition of organic layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
    • 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
    • C23C14/12—Organic material
    • 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
    • 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
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • 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
    • C23C16/44—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
    • C23C16/513—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 using plasma jets
    • 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
    • C23C16/52—Controlling or regulating the coating process
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/0416—Control or interface arrangements specially adapted for digitisers
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

Definitions

  • the invention belongs to the field of chemical coatings, and specifically relates to a DLC coating, its preparation method and equipment, composite coatings and coated products.
  • Japan's Daikin proposed the technology of evaporating fluoride pills, which has greatly improved wear resistance and anti-fingerprint, and has been widely recognized in the industry .
  • AF anti-fingerprint
  • Japan's Daikin proposed the technology of evaporating fluoride pills, which has greatly improved wear resistance and anti-fingerprint, and has been widely recognized in the industry .
  • the wear resistance requirements for smart touch panels continue to increase, and the original technical bottlenecks need to be broken through.
  • DLC (diamond-like coating) coating is a hybrid of carbon allotropes. It combines the hard and wear-resistant properties of diamond with the flexible and lubricating properties of graphite, giving DLC coating a wide range of properties.
  • Application possibilities are the two main problems that limit the application of DLC coatings on touch panels (PC, glass, PMMA, etc.) are the color difference of the film layer, which affects the light transmittance, and the other problem is the bonding strength of the film layer, which is bonded to the substrate. The bonding strength with the subsequent plating of the oleophobic layer requires attention. In recent years, scientific researchers have improved the overall performance of the film by doping new elements into DLC coatings.
  • the main doped elements include Ti, Cr, Zr, Si, N, etc.
  • the friction coefficient can be obtained by preparing silicon-doped DLC coatings by DC magnetron sputtering, medium frequency magnetron sputtering and ion source-assisted deposition. Lower diamond-like coating.
  • this method needs to combine multiple discharge modes at the same time.
  • the equipment structure is relatively complex and the manufacturing cost is high.
  • the coating temperature is greater than 150°C.
  • the deposition temperature is higher than conventional touch panel materials such as PMMA, PC and other polymer materials. The maximum heat deformation temperature cannot meet the needs of industrialized and stable production in the field of touch panels.
  • the specific embodiment of the present invention provides a DLC coating prepared by PECVD (Plasma Enhanced Chemical Vapor Deposition) method that is simple to prepare and is conducive to process production with low color difference, high transparency and high bonding strength. And the anti-fingerprint composite coating thus prepared has low color difference, high transparency and more scratch resistance.
  • PECVD Plasma Enhanced Chemical Vapor Deposition
  • the specific plan is as follows:
  • a DLC coating is deposited by a PECVD method from a hydrocarbon monomer of C x1 H y1 and a silane monomer of C x2 H y2 Si z , where x1 is an integer from 1 to 10, y1 is an integer from 2 to 22, x2 is an integer from 0 to 32, y2 is an integer from 4 to 68, and z is an integer from 1 to 4.
  • the boiling point of the hydrocarbon monomer and silane monomer is below 100°C under normal pressure.
  • the hydrocarbon monomer is methane, acetylene, benzene or ethylene.
  • the silane monomer is silane, methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, ethylsilane or diethylsilane.
  • the molar ratio of the hydrocarbon monomer to the silane monomer is 60:40 to 95:5.
  • the thickness of the DLC coating is 5-100 nm.
  • a preparation device for DLC coating as described above, the device includes:
  • Plasma reactor for depositing DLC coatings by PECVD method
  • Monomer vaporization control device used to heat and vaporize hydrocarbon monomers that are liquid at room temperature or control the vaporization state of silane monomers
  • Gas flow meter used to measure and control the monomer flow after gasification
  • Thermal insulation device is used to insulate the monomer flow line to ensure that the gasified monomer in the monomer gasification control device flows stably into the plasma reactor.
  • the device further includes a pressure gauge disposed between the monomer gasification control device and the gas flow meter, and the temperature of the monomer gasification control device can be controlled based on the pressure gauge reading.
  • a method for preparing a DLC coating as described above including the following steps:
  • the gases of the hydrocarbon monomer and silane monomer are metered into the plasma reactor, the bias power supply is turned on, and the PECVD method is used to deposit a DLC coating on the substrate.
  • the hydrocarbon monomer and silane monomer are measured in the form of gas through a gas flow meter.
  • the temperature of the silane monomer is controlled, and the pressure of the silane monomer gas is controlled between 0.001MPa and 0.003MPa.
  • the flow rate of the hydrocarbon monomer is 10-200 sccm
  • the flow rate of the silane monomer is 5-100 sccm.
  • an inert gas is introduced, and the flow rate of the inert gas is 20-200 sccm.
  • the pressure in the plasma reactor is 15-100mT
  • the bias voltage input is -200 to -800V
  • the coating deposition time is 2-30min.
  • a composite coating which includes a DLC coating as described above and an AF coating formed on the DLC coating.
  • the raw material of the AF coating includes perfluoropolyether polymer.
  • the perfluoropolyether polymer is perfluoropolyether silane or perfluoropolyether alkoxysilane.
  • the thickness of the AF coating is 5-20 nm.
  • the AF coating is deposited by vacuum evaporation.
  • the product is a touch panel.
  • the color difference of the coated product before and after coating is less than 0.5.
  • the coated surface substrate of the product is glass.
  • the speed is 40cycle/min
  • the test direction is the same as the fiber direction of the steel wool
  • the test stroke is 40mm. Observe that the water drop angle is above 100°.
  • the coated surface substrate of the product is plastic.
  • the speed is 40cycle/min
  • the test direction is the same as the fiber direction of the steel wool
  • the test stroke is 40mm. Observe that the water drop angle is above 100°.
  • the DLC coating is deposited by the PECVD method from hydrocarbon monomers and silane monomers, and can be reacted and deposited at room temperature to form a coating, effectively avoiding the higher temperatures in conventional coating methods. Impact on the performance of the substrate. Furthermore, the DLC coating formed by the specific embodiment of the present invention has the characteristics of low color difference, high transparency and high bonding strength, and its preparation method is simple, which is conducive to process production. Furthermore, in the The anti-fingerprint composite coating obtained by depositing AF coating on DLC coating has low color difference, high transparency and more scratch resistance, and is especially suitable for coated products such as touch panels.
  • Figure 1 is a schematic diagram of a DLC coating preparation device according to a specific embodiment of the present invention.
  • a specific embodiment of the present invention provides a DLC coating.
  • the DLC coating is formed by depositing a hydrocarbon monomer of C x1 H y1 and a silane monomer of C x2 H y2 Siz through a PECVD method, where x1 is An integer from 1 to 10, y1 is an integer from 2 to 22, x2 is an integer from 0 to 32, y2 is an integer from 4 to 68, z is an integer from 1 to 4.
  • the DLC coating of the specific embodiment of the present invention uses the PECVD method for silicon element doping, and can be reactively deposited at room temperature to form a coating, effectively avoiding the impact of higher temperatures on the performance of the substrate under conventional coating methods.
  • it can be very good It is suitable for PC, PMMA and other polymer materials commonly used in touch panels.
  • it innovatively applies silicon-doped technology to touch panels, which can solve the problem of DLC easily turning yellow and discolored.
  • the boiling points of the hydrocarbon monomers and silane monomers under normal pressure are below 100°C, and using monomers with boiling points below 100°C can be easily controlled.
  • the vaporization state of the monomer can better and continuously control the ratio of hydrocarbon monomer and silane monomer by controlling the gas monomer flow rate, thereby accurately controlling the ratio of carbon, hydrogen and silicon in DLC, thereby better ensuring The hardness, low color difference and high transparency of DLC coating.
  • x1 is an integer from 1 to 4
  • y1 is an integer from 2 to 10
  • x2 is an integer from 0 to 16
  • y2 is an integer from 4 to 36.
  • z is 1.
  • the hydrocarbon monomer can be an alkyne such as acetylene or propyne, an alkene such as ethylene or propylene, or an alkane such as methane, ethane or propane, etc. , it can also be aromatic hydrocarbons such as benzene, and the hydrocarbon monomer can be one or more.
  • the molar ratio of the hydrocarbon monomer to the silane monomer is 60:40 to 95:5. Specifically, it can be 60:40 or 65: 35, 70:30, 75:25, 80:20, 85:15, 90:10 or 95:5 etc.
  • the thickness of the DLC coating is 5-100nm. Specific examples include 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm or 100nm and so on.
  • a specific embodiment of the present invention also provides a device for preparing the DLC coating as described above, which device includes:
  • Plasma reactor for depositing DLC coatings by PECVD method
  • Monomer vaporization control device used to heat and vaporize hydrocarbon monomers that are liquid at room temperature or control the vaporization state of silane monomers
  • Gas flow meter used to measure and control the monomer flow after gasification
  • Thermal insulation device is used to insulate the monomer flow line to ensure that the gasified monomer in the monomer gasification control device flows stably into the plasma reactor.
  • FIG. 1 a schematic diagram of a DLC coating preparation device according to a specific embodiment of the present invention.
  • the device includes:
  • Plasma reactor 1 used to deposit DLC coating by PECVD method
  • Monomer vaporization control device used to heat and vaporize hydrocarbon monomers that are liquid at room temperature or control the vaporization state of silane monomers
  • the first gas flow meter 6 is used to accurately measure and control the flow rate of the gasified monomer; the insulation device is used to insulate the monomer flow line to ensure that the gasified monomer flows into the plasma reactor 1 In the process of gasification.
  • the monomer gasification control device includes a monomer container 2 and a temperature control device 3.
  • the monomer container 2 The monomer in is a hydrocarbon monomer that is liquid at normal temperature.
  • the monomer container 2 is heated by the temperature control device 3 to vaporize the hydrocarbon monomer that is liquid at normal temperature, so that it can pass through the first gas flow meter 6 Accurately measure the amount of the hydrocarbon monomer that is liquid at room temperature.
  • the monomer in the monomer container 2 is a silane monomer
  • the temperature control device 3 is used to make the monomer container 2 at an appropriate temperature. temperature state, so that the input amount of the silane monomer can be accurately measured through the first gas flow meter 6.
  • the temperature control device 3 is a water bath or oil bath device.
  • a pressure gauge 4 is provided between the monomer gasification control device and the first gas flow meter 6, which can be controlled according to the reading of the pressure gauge.
  • the temperature of the monomer gasification control device for example, in some specific embodiments, is monitored by the pressure gauge 4 and the temperature of the temperature control device 3 is adjusted to control the pressure between 0.001MPa and 0.003MPa.
  • the DLC coating preparation device of the specific embodiment of the present invention.
  • the DLC coating preparation device further includes a second gas flow meter 7 for accurately metering and controlling hydrocarbon monomers that are gases at room temperature, such as Flow rate of methane, ethylene or acetylene etc.
  • the DLC coating preparation device in some specific embodiments, has multiple hydrocarbon monomers and silane monomers that are liquid at room temperature, corresponding to the monomer vaporization control device and the first gas There are multiple flow meters 6 correspondingly set.
  • the DLC coating preparation device of the specific embodiment of the present invention is often There are a plurality of hydrocarbon monomers that are gases at room temperature, and a plurality of corresponding second gas flow meters 7 are provided.
  • the DLC coating preparation device in some specific embodiments, also includes another second gas flow meter 7 for metering in inert carrier gas, such as helium or argon.
  • inert carrier gas such as helium or argon.
  • the DLC coating preparation device of the specific embodiment of the present invention also includes a gas mixing device 5 , which is used to mix multiple monomer gases evenly before entering the plasma reactor 1 .
  • the DLC coating preparation device of the specific embodiment of the present invention can accurately control the proportion of carbon, hydrogen and silicon in the DLC coating by controlling the flow rate of vaporized monomers, especially the flow rate of silane vaporized monomers. , thereby better ensuring the hardness, low color difference and high transparency of the DLC coating.
  • Specific embodiments of the present invention also provide a preparation method for the DLC coating as described above, which includes the following steps:
  • the gases of the hydrocarbon monomer and silane monomer are metered into the plasma reactor, the bias power supply is turned on, and the PECVD method is used to deposit a DLC coating on the substrate.
  • the material of the substrate is metal, ceramics, plastic or glass, etc.
  • the substrate is a touch panel.
  • the substrate is cleaned, for example, in some specific embodiments, Before DLC coating, pass in 0-200sccm argon and/or 0-200sccm oxygen, control the pressure at 15-100mT, turn on the bias power supply, feed -300 to -1000V voltage, and bombard and clean the substrate for 5-20 minutes. Contaminants such as oxides on the surface of the product substrate are etched cleanly, forming a high surface energy interface, providing a good deposition foundation for DLC.
  • the gas flow meter is directly used to accurately measure the gas at room temperature.
  • the input amount of gaseous hydrocarbon monomers For hydrocarbon monomers that are liquid at room temperature, they are first heated and vaporized, and the input amount of hydrocarbon monomers that are liquid at room temperature is accurately measured by a gas flow meter.
  • silane Monomer by controlling its temperature and pressure between 0.001MPa and 0.003MPa, and then accurately measuring the input amount of the silane monomer through a gas flow meter, thereby accurately controlling the monomer ratio to accurately control the DLC coating
  • the proportion of carbon, hydrogen and silicon in the coating can better ensure the hardness, low color difference and high transparency of the DLC coating.
  • the flow rate of the hydrocarbon monomer is 10-200 sccm
  • the flow rate of the silane monomer is 5-100 sccm
  • the hydrocarbon monomer and The molar ratio of silane monomer is between 60:40 and 95:5.
  • Specific examples include 60:40, 65:35, 70:30, 75:25, 80:20, 85:15, 90:10 or 95: 5, etc.
  • the specific molar ratio of hydrocarbon monomers and silane monomers can be adjusted and controlled according to the substrate material, specific hydrocarbon monomers and silane monomers, and actual needs.
  • inert gas such as argon or neon is introduced simultaneously with the monomer gas, and the flow rate of the inert gas is 20-200 sccm.
  • the pressure in the plasma reactor is 15-100mT
  • the bias voltage input is -200 to -800V
  • the coating deposition time is 2- 30 minutes.
  • Specific embodiments of the present invention also provide a composite coating, which includes a DLC coating as described above and an AF coating formed on the DLC coating.
  • the composite coating of the specific embodiment of the present invention provides a good connection point for the AF coating.
  • the process of plating silicon dioxide before the AF coating can be eliminated and AF can be obtained.
  • the excellent bonding strength with the touch panel, and the hardness of the DLC coating ( ⁇ 1500HV) is higher than that of silicon dioxide ( ⁇ 1100HV), which can further improve the mechanical durability of the AF coating and significantly increase the AF coating's Friction resistant effect.
  • the AF coating is a commonly used AF coating raw material.
  • the raw material of the AF coating is a fluorinated material, such as perfluoropolyether polymer or other suitable fluorinated materials.
  • the perfluoropolyether polymer is a perfluoropolyether silane or a perfluoropolyether alkoxysilane.
  • the perfluoropolyether polymer can be UD509 manufactured by Daikin Industrial Co., Ltd., KY-178, KY-185, KY-1900 manufactured by Shin-Etsu Chemical Industry Co., Ltd., Solvay Fomblin of the company (SOLVAY) and so on.
  • the thickness of the AF coating is 5-20 nm, specifically, it can be 5 nm, 10 nm, 15 nm or 20 nm, etc.
  • the AF coating is formed by vacuum evaporation. In some specific implementations, the AF coating can also be formed by other methods such as spray electroplating. way to form.
  • Specific embodiments of the present invention also provide a coated article, at least part of the surface of the coated article has the composite coating as described above.
  • the product is a touch panel, such as a touch panel including a mobile phone, tablet, car, TV or LED, etc.
  • the products are electrical products, construction products or any products that require transparency, scratch resistance or abrasion resistance.
  • the color difference of the coated product before and after coating is less than 0.5. In some specific embodiments, the color difference of the coated product before and after coating is less than 0.5. The color difference difference is less than 0.4. In some embodiments, the color difference difference of the coated product before and after coating is less than 0.3.
  • the coated products of specific embodiments of the present invention have excellent wear resistance.
  • the coated surface substrate of the product is glass.
  • the speed is 40cycle/min
  • the test direction is the same as the fiber direction of steel wool
  • the test stroke is 40mm
  • the observed water drop angle is above 100°.
  • the coated surface substrate of the product is glass, according to the steel wool Test, after withstanding 7000 reciprocating cycles with a load of 10N, the speed is 40cycle/min, the test direction is the same as the fiber direction of steel wool, the test stroke is 40mm, and the water drop angle is observed to be above 100°.
  • the product Paint The base material of the covered surface is glass.
  • the speed is 40cycle/min
  • the test direction is the same as the fiber direction of the steel wool
  • the test stroke is 40mm
  • the water drop angle is observed to be above 100°.
  • the coated surface substrate of the product is plastic.
  • the speed is 40cycle/min
  • the test direction is the same as the fiber direction of the steel wool
  • the test stroke is 40mm. , observe that the water drop angle is above 100°.
  • the coated surface base material of the product is plastic.
  • the speed is 40cycle/min
  • the test direction and The fiber directions of steel wool are the same
  • the test stroke is 40mm
  • the water drop angle is observed to be above 100°.
  • the coated surface base material of the product is plastic. According to the steel wool test, it withstands 1000 reciprocating cycles with a 1N load. After that, the speed is 40cycle/min, the test direction is the same as the fiber direction of steel wool, the test stroke is 40mm, and the water drop angle is observed to be above 100°.
  • Coating water drop angle tested according to GB/T 30447-2013 standard.
  • Coating transmittance and color difference Calculated according to GB11186.3-1989 standard, using KONICA spectrometer CM-5, and selecting C light source for detection. ⁇ E in the test results represents color difference.
  • T represents the light transmittance;
  • L, a, and b represent the three color channels in the Lab color model, L represents the brightness, a represents red and green, and b represents yellow and blue.
  • Wear resistance test Taber5900 reciprocating friction machine, Bonstar#0000 steel wool, 10N load for glass substrate/1N load for plastic substrate, speed 40cycle/min, test direction is the same as the fiber direction of steel wool, test stroke 40mm, observation The number of times the water drop angle is less than 100°.
  • the vacuum pump set When the vacuum pressure is less than 0.05mT, 100 sccm argon gas is introduced, and the pressure Control it at 30mT, turn on the bias power, feed -400V voltage, and bombard and clean the substrate for 5 minutes. Then turn off the power and gas source, and open the water bath at the same time to control the water bath temperature to 26°C. At this temperature, the tetramethylsilane monomer gas pressure value is controlled between 0.001MPa and 0.003MPa.
  • Adjust the gas flow valve to control the flow rate of tetramethylsilane monomer to 40 sccm, the argon flow rate to 100 sccm, and the methane flow rate to 80 sccm. Pass them into the gas mixer to mix and then pass them into the plasma reactor.
  • the chamber pressure of the plasma reactor Control at 30mT, turn on the bias power, input voltage to -300V, coating time is 10 minutes, and obtain a layer of 20nm highly transparent and high hardness DLC coating. Then turn off the power supply, gas source and pump group in sequence, and open the cavity of the plasma reactor. Take out the glass touch panel from the chamber door.
  • Example 1 The glass touch panel in Example 1 was changed to a PC touch panel, the 100 sccm argon gas introduced in the substrate cleaning step was changed to 100 sccm oxygen, the cleaning time was extended to 20 minutes, and other process steps remained unchanged.
  • DLC-coated and AF-coated PC touch panels were tested for light transmittance, color difference, and wear resistance. The results are listed in Table 1 below.
  • Example 1 The glass touch panel in Example 1 was changed to a PMMA touch panel. The etching and cleaning time was shortened to 2 minutes. The other process steps remained unchanged. The PMMA touch panel with DLC coating and AF coating deposited in sequence was light-transmitted. Rate, color difference and wear resistance testing, the results are listed in Table 1 below.
  • Example 1 The water bath temperature in Example 1 was set to 10°C, the tetramethylsilane monomer was replaced with trimethylsilane monomer, and other process step parameters remained unchanged.
  • the glass touch panel with DLC coating and AF coating deposited in sequence was The panel was tested for light transmittance, color difference and wear resistance, and the results are listed in Table 1 below.
  • the impurities in the chamber are discharged through the vacuum pump set.
  • the vacuum pressure is less than 0.05mT, 100 sccm argon gas is introduced, and the pressure Control it at 30mT, turn on the bias power supply, feed -400V voltage, bombard and clean the substrate for 5 minutes, take it out, and put it into the evaporation chamber.
  • pump the vacuum bottom pressure to below 4.0 ⁇ 10 -3 Pa, and then fill it with silicon dioxide.
  • the evaporation boat current is set to 30A and the time is 120s.
  • a layer of 20nm silicon dioxide layer is evaporated, then the vacuum is pumped to 3.0 ⁇ 10 -3 Pa, and the UD509AF liquid is passed into another evaporation boat.
  • the evaporation boat current is 12A.
  • Time 800s evaporate a layer of 10nm AF coating, and then take out the glass touch panel.
  • the coated glass touch panel was tested for light transmittance, color difference and wear resistance, and the results are listed in Table 1 below.
  • Example 1 Set the flow rate of the tetramethylsilane monomer in Example 1 to zero, extend the coating time to 15 minutes, and keep other process step parameters unchanged.
  • a layer of 20nm DLC coating is obtained by plating, and then 10nm AF is prepared under the same process conditions. coating.
  • the light transmittance, color difference and wear resistance of the glass touch panel with DLC coating and AF coating deposited in sequence were tested. The results are listed in Table 1 below.
  • the glass touch panel was only purged with dry nitrogen, without coating, and the light transmittance was tested. The results are listed in Table 1 below.
  • the PC touch panel was only purged clean with dry nitrogen, without coating, and the light transmittance was tested. The results are listed in Table 1 below.
  • the PMMA touch panel was only purged clean with dry nitrogen, without coating, and the light transmittance was tested. The results are listed in Table 1 below.
  • the coated glass touch panels of Example 1 and Example 4 and the uncoated glass touch panel of Comparative Example 4 have basically the same light transmittance.
  • the coated PC of Example 2 The touch panel has basically the same light transmittance as the uncoated PC touch panel of Comparative Example 5.
  • the coated PMMA touch panel of Example 3 has basically the same light transmittance as the uncoated PMMA touch panel of Comparative Example 6.
  • the light transmittance shows that the DLC coating and the composite coating of the present invention have excellent light transmittance; the friction resistance times of Example 1 are much higher than those of Comparative Examples 1 and 2, indicating that the composite coating of the present invention has excellent light transmittance.
  • the composite coating has more excellent scratch resistance; compared with Example 1, the DLC coating in Comparative Example 3 did not pass tetramethylsilane monomer into it.
  • Si is doped
  • the transmittance is significantly reduced
  • the color difference is significantly increased
  • the wear resistance is sharply reduced, indicating that the composite coating obtained by depositing the AF coating on the DLC coating of the present invention has low color difference, high transparency, and is more scratch-resistant. Rubbing characteristics.

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Abstract

一种DLC涂层、其制备方法及设备及复合涂层、涂覆制品，DLC涂层由碳氢单体和硅烷单体以PECVD方法沉积，可在室温下反应沉积形成涂层，有效避免了常规镀膜方式下较高温度对基材性能的影响，形成的DLC涂层具有低色差、高透明和高结合强度的特性，并且制备方法简单，有利于工艺生产，在DLC涂层沉积AF涂层所获得的复合涂层具有低色差、高透明以及更加耐刮擦的特性，特别适用于触控面板等涂覆制品。

Description

一种DLC涂层、其制备方法及设备及复合涂层、涂覆制品
本申请要求于2022年4月15日提交中国专利局、申请号为202210395178.5、发明名称为“一种DLC涂层、其制备方法及设备及复合涂层、涂覆制品”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于化学涂层领域，具体涉及一种DLC涂层、其制备方法及设备及复合涂层、涂覆制品。
背景技术
近年来随着互联网技术和工业制造技术不断地推陈更新，人们日常生活已经进入到了多媒体时代，生活和工作场所随处可见的触摸操控屏，各类新颖的可穿戴电子设备，给日常的生活和工作带来了极大的趣味性和便利性。随着触摸控制的普及，其本身存在的易磨花和容易黏附指纹的特性，一方面影响观感，另一方面也会影响到功能使用，带来较差的使用体验感，所以需要在其表面形成一层AF(anti-fingerprint)涂层(防指纹涂层)，日本大金提出了蒸镀氟化药丸的技术，带来了极大的耐磨防指纹的提升，得到了行业内广泛认可。但随着使用需求的不断增加以及应用场景的更新，对智能触控面板的耐磨要求不断提高，原先的技术瓶颈就需求去突破。
DLC(diamond-like coating)涂层(类金刚石涂层)是由碳的同素异构体杂合而成，结合金刚石的坚硬耐磨和石墨的柔韧润滑的特性，赋予了DLC涂层广泛的应用可能性。但在触控面板上(PC、玻璃、PMMA等)限制DLC涂层运用的两个主要问题是膜层有色差，影响透光率，另一个问题是膜层结合强度的问题，与基材结合和后续镀制疏油层的结合强度都是需要关注的。近年来，科研工作者通过向DLC涂层中掺杂新元素，从而提高膜层的综合性能，主要掺杂的元素有Ti、Cr、Zr、Si、N等。例如通过直流磁控溅射、中频磁控溅射以及离子源辅助的沉积方式制备掺硅DLC涂层，可以获得摩擦系数 较低的类金刚石涂层。该方法一方面需要同时复合多种放电方式，设备结构比较复杂，制造成本高，另一方面镀膜温度大于150℃，该沉积温度都高于常规的触控面板材料像PMMA、PC等高分子材料的最高热变形温度，无法满足在触控面板领域的工业化稳定生产需求。
发明内容
本发明的具体实施方式提供一种由PECVD(Plasma Enhanced Chemical Vapor Deposition，等离子体增强化学气相沉积)方法制备的制备简单、有利于工艺生产的低色差、高透明和高结合强度的DLC涂层，以及由此制备的具有低色差、高透明以及更加耐刮擦特性的防指纹复合涂层，具体方案如下：
一种DLC涂层，所述DLC涂层为由Cx1Hy1的碳氢单体和Cx2Hy2Siz的硅烷单体通过PECVD方法沉积形成，其中，x1为1到10的整数，y1为2到22的整数，x2为0到32的整数，y2为4到68的整数，z为1到4的整数。
可选的，常压下所述碳氢单体和硅烷单体的沸点在100℃以下。
可选的，所述碳氢单体为甲烷、乙炔、苯或乙烯。
可选的，所述硅烷单体为硅烷、甲基硅烷、二甲基硅烷、三甲基硅烷、四甲基硅烷、乙基硅烷或二乙基硅烷。
可选的，所述碳氢单体与硅烷单体的摩尔比在60:40～95:5。
可选的，所述DLC涂层的厚度为5-100nm。
一种如上所述DLC涂层的制备装置，所述装置包括：
等离子体反应器，用于通过PECVD方法沉积形成DLC涂层；
单体气化控制装置，用于将常温下为液体的碳氢单体加热气化或者控制硅烷单体的气化状态；
气体流量计，用于计量控制气化后的单体流量；
保温装置，用于对单体流动线路保温，以保证所述单体气化控制装置中的气化单体稳定通入所述等离子体反应器。
可选的，所述装置还包括设置于单体气化控制装置与气体流量计之间的压力表，可根据所述压力表读数控制单体气化控制装置的温度。
一种如上所述DLC涂层的制备方法，包括以下步骤：
提供基材，将基材置于等离子体反应器中；
将所述碳氢单体和硅烷单体的气体计量通入所述等离子体反应器中，开启偏压电源，采用PECVD方法在所述基材上沉积DLC涂层。
可选的，所述碳氢单体和硅烷单体分别以气体的形式由气体流量计计量通入。
可选的，控制所述硅烷单体温度，将所述硅烷单体气体的压力控制在0.001MPa到0.003MPa之间。
可选的，所述碳氢单体的流量为10-200sccm，硅烷单体的流量为5-100sccm。
可选的，通入单体气体的同时通入惰性气体，所述惰性气体的流量为20-200sccm。
可选的，等离子体反应器中的压力为15-100mT，偏压电压输入为-200至-800V，涂层沉积时间为2-30min。
一种复合涂层，所述复合涂层包括如上所述DLC涂层以及形成于所述DLC涂层上的AF涂层。
可选的，所述AF涂层的原材料包括全氟聚醚聚合物。
可选的，所述全氟聚醚聚合物为全氟聚醚硅烷或全氟聚醚烷氧基硅烷。
可选的，所述AF涂层的厚度为5-20nm。
可选的，通过真空蒸镀的方法沉积形成所述AF涂层。
一种涂覆制品，所述涂覆制品的至少部分表面具有如上所述的复合涂层。
可选的，所述制品为触控面板。
可选的，所述涂覆制品在涂覆前后的色差差值在0.5以下。
可选的，所述制品的涂覆表面基材为玻璃，根据钢丝绒测试，用10N载荷经受6000次往复循环之后，速度40cycle/min，测试方向和钢丝绒的纤维方向相同，测试行程40mm，观察水滴角在100°以上。
可选的，所述制品的涂覆表面基材为塑料，根据钢丝绒测试，用1N载荷经受800次往复循环之后，速度40cycle/min，测试方向和钢丝绒的纤维方向相同，测试行程40mm，观察水滴角在100°以上。
本发明具体实施方式的DLC涂层，所述DLC涂层为由碳氢单体和硅烷单体以PECVD方法沉积，可在室温下反应沉积形成涂层，有效避免了常规镀膜方式下较高温度对基材性能的影响，进一步，本发明具体实施方式的形成的DLC涂层具有低色差、高透明和高结合强度的特性，并且其制备方法简单，有利于工艺生产，更进一步，在所述DLC涂层沉积AF涂层所获得的防指纹复合涂层具有低色差、高透明以及更加耐刮擦的特性，特别适用于触控面板等涂覆制品。
附图说明
图1为本发明一具体实施方式的DLC涂层的制备装置示意图。
具体实施方式
本发明的具体实施方式提供一种DLC涂层，所述DLC涂层为由Cx1Hy1的碳氢单体和Cx2Hy2Siz的硅烷单体通过PECVD方法沉积形成，其中，x1为1到10的整数，y1为2到22的整数，x2为0到32的整数，y2为4到68的整数，z为1到4的整数。
本发明具体实施方式的DLC涂层，利用PECVD的方法进行硅元素掺杂，可在室温下反应沉积形成涂层，有效避免常规镀膜方式下较高温度对基材性能的影响，例如可很好的适用于PC、PMMA等常规用于触控面板的高分子材料上，同时创新性的将掺硅技术运用到触摸面板上，可解决DLC容易泛黄异色的现象。
本发明具体实施方式的DLC涂层，在一些具体实施方式中，常压下所述碳氢单体和硅烷单体的沸点在100℃以下，使用沸点在100℃以下的单体，可以容易控制单体的气化状态，从而可以更好的通过控制气体单体流量精确持续控制碳氢单体与硅烷单体的比例，从而精确控制DLC中碳、氢和硅的比例，从而更好的保证DLC涂层的硬度、低色差及高透明特性。
本发明具体实施方式的DLC涂层，在一些具体实施方式中，所述x1为1到4的整数，y1为2到10的整数，x2为0到16的整数，y2为4到36的整数，z为1。
本发明具体实施方式的DLC涂层，在一些具体实施方式中，所述碳氢单体可以是炔烃例如乙炔或丙炔等，烯烃例如乙烯或丙烯等，烷烃例如甲烷、乙烷或丙烷等，也可是芳香烃例如苯，所述碳氢单体可以是一种也可以是多种。
本发明具体实施方式的DLC涂层，在一些具体实施方式中，所述碳氢单体与硅烷单体的摩尔比在60:40～95:5，具体的例如可以是60:40、65:35、70:30、75:25、80:20、85:15、90:10或95:5等等。
本发明具体实施方式的DLC涂层，在一些具体实施方式中，所述DLC涂层的厚度为5-100nm，具体的例如可以是5nm、10nm、15nm、20nm、25nm、30nm、35nm、40nm、45nm、50nm、55nm、60nm、65nm、70nm、75nm、80nm、85nm、90nm、95nm或100nm等等。
本发明的具体实施方式还提供一种如上所述DLC涂层的制备装置，所述装置包括：
等离子体反应器，用于通过PECVD方法沉积形成DLC涂层；
单体气化控制装置，用于将常温下为液体的碳氢单体加热气化或者控制硅烷单体的气化状态；
气体流量计，用于计量控制气化后的单体流量；
保温装置，用于对单体流动线路保温，以保证所述单体气化控制装置中的气化单体稳定通入所述等离子体反应器。
以下参考附图1进一步对本发明具体实施方式的DLC涂层制备装置进行说明，如附图1本发明一具体实施方式的DLC涂层制备装置示意图，本发明 具体实施方式的DLC涂层的制备装置，所述装置包括：
等离子体反应器1，用于通过PECVD方法沉积形成DLC涂层；
单体气化控制装置，用于将常温下为液体的碳氢单体加热气化或者控制硅烷单体的气化状态；
第一气体流量计6，用于精确计量控制气化后的单体流量；保温装置，用于对单体流动线路保温，以保证气化后的单体通入所述等离子体反应器1的过程中处于气化状态。
本发明具体实施方式的DLC涂层制备装置，在一些具体实施方式中，所述单体气化控制装置，包括单体容器2和温度控制装置3，在一些具体实施方式中，单体容器2中的单体为常温下为液体的碳氢单体，通过温度控制装置3对单体容器2加热使常温下为液体的碳氢单体气化，从而可通过所述第一气体流量计6精确计量所述常温下为液体的碳氢单体的通入量，在一些具体实施方式中，单体容器2中的单体为硅烷单体，通过温度控制装置3使单体容器2处于合适的温度状态，从而可通过所述第一气体流量计6精确计量所述硅烷单体的通入量，在一些具体实施方式中，所述温度控制装置3为水浴或油浴装置。
本发明具体实施方式的DLC涂层制备装置，在一些具体实施方式中，所述单体气化控制装置与第一气体流量计6之间设置有压力表4，可根据所述压力表读数控制单体气化控制装置的温度，例如在一些具体实施方式中，通过对压力表4监控，调节温度控制装置3的温度，将压力控制在0.001MPa到0.003MPa之间。
本发明具体实施方式的DLC涂层制备装置，在一些具体实施方式中，所述DLC涂层制备装置还包括第二气体流量计7，用于精确计量控制常温下为气体的碳氢单体例如甲烷、乙烯或乙炔等的流量。
本发明具体实施方式的DLC涂层制备装置，在一些具体实施方式中，常温下为液体的碳氢单体和硅烷单体具有多个，对应的所述单体气化控制装置和第一气体流量计6对应设置为多个。
本发明具体实施方式的DLC涂层制备装置，在一些具体实施方式中，常 温下为气体的碳氢单体具有多个，对应的所述第二气体流量计7对应设置为多个。
本发明具体实施方式的DLC涂层制备装置，在一些具体实施方式中，还包括另外一个第二气体流量计7，用于计量通入惰性载气，例如氦气或氩气等。
本发明具体实施方式的DLC涂层制备装置，在一些具体实施方式中，还包括气体混合装置5，所述气体混合装置用于将多种单体气体在进入等离子体反应器1之前混合均匀。
本发明具体实施方式的DLC涂层制备装置，可通过控制气化单体流量特别是硅烷气化单体流量的方式精确控制单体比例来精确控制DLC涂层中的碳、氢和硅的比例，从而更好的保证DLC涂层的硬度、低色差及高透明特性。
本发明的具体实施方式还提供一种如上所述DLC涂层的制备方法，包括以下步骤：
提供基材，将基材置于等离子体反应器中；
将所述碳氢单体和硅烷单体的气体计量通入所述等离子体反应器中，开启偏压电源，采用PECVD方法在所述基材上沉积DLC涂层。
本发明具体实施方式的DLC涂层的制备方法，在一些具体实施方式中，所述基材的材质为金属、陶瓷、塑料或玻璃等。
本发明具体实施方式的DLC涂层的制备方法，在一些具体实施方式中，所述基材为触控面板。
本发明具体实施方式的DLC涂层的制备方法，在一些具体实施方式中，为进一步增强等离子体涂层与基材的结合力，对基材进行清洁处理，例如在一些具体实施方式中，在DLC涂层前，通入0-200sccm氩气和/或0-200sccm氧气，压力控制在15-100mT，打开偏压电源，馈入-300至-1000V电压，轰击清洗基材5-20min，将产品基材表面氧化物等污染物刻蚀干净，形成高表面能的界面，为DLC提供良好的沉积基础。
本发明具体实施方式的DLC涂层的制备方法，在一些具体实施方式中，对于常温下为气体的碳氢单体，直接通过气体流量计精确计量所述常温下为 气体的碳氢单体的通入量，对于常温下为液体的碳氢单体先加热气化，通过气体流量计精确计量所述常温下为液体的碳氢单体的通入量，对于硅烷单体，通过控制其温度，控制其压力在0.001MPa到0.003MPa之间，进而通过气体流量计精确计量所述硅烷单体的通入量，以此精确控制单体比例来精确控制DLC涂层中的碳、氢和硅的比例，从而更好的保证DLC涂层的硬度、低色差及高透明特性。
本发明具体实施方式的DLC涂层的制备方法，在一些具体实施方式中，所述碳氢单体的流量为10-200sccm，硅烷单体的流量为5-100sccm，所述碳氢单体与硅烷单体的摩尔比在60:40～95:5，具体的例如可以是60:40、65:35、70:30、75:25、80:20、85:15、90:10或95:5等等，具体的碳氢单体与硅烷单体的摩尔比可以根据基材材质、具体碳氢单体与硅烷单体以及实际需求等进行调节来控制。
本发明具体实施方式的DLC涂层的制备方法，在一些具体实施方式中，通入单体气体的同时通入惰性气体例如氩气或氖气等，所述惰性气体的流量为20-200sccm。
本发明具体实施方式的DLC涂层的制备方法，在一些具体实施方式中，等离子体反应器中的压力为15-100mT，偏压电压输入为-200至-800V，涂层沉积时间为2-30min。
本发明具体实施方式的DLC涂层的制备方法，所述碳氢单体与硅烷单体的说明如前所述。
本发明的具体实施方式还提供一种复合涂层，所述复合涂层包括如上所述DLC涂层以及形成于所述DLC涂层上的AF涂层。
本发明具体实施方式的复合涂层，掺杂Si元素的所述DLC涂层，为AF涂层提供了良好的连接点位，可以取消AF涂层前镀制二氧化硅的工艺也可获得AF与触控面板的优异结合强度，同时所述DLC涂层的硬度(～1500HV)高于二氧化硅的硬度(～1100HV)，可以进一步提高AF涂层的机械耐久性，显著增加AF涂层的耐摩擦效果。
本发明具体实施方式的复合涂层，在一些具体实施方式中，所述AF涂层 的原材料为常用的AF涂层原材料，例如，在一些具体实施方式中，所述AF涂层的原材料为氟化材料，例如全氟聚醚聚合物或者其他合适的氟化材料。在一些具体实施方式中，所述全氟聚醚聚合物为全氟聚醚硅烷或全氟聚醚烷氧基硅烷。具体的，在一些具体实施方式中，所述全氟聚醚聚合物可以是大金工业株式会社制的UD509、信越化学工业株式会社制的KY-178、KY-185、KY-1900、苏威公司(SOLVAY)的Fomblin等等。
本发明具体实施方式的复合涂层，在一些具体实施方式中，所述AF涂层的厚度为5-20nm，具体的例如可以是5nm、10nm、15nm或20nm等等。
本发明具体实施方式的复合涂层，在一些具体实施方式中，所述AF涂层采用真空蒸镀的方式形成，在一些具体方式中，所述AF涂层也可以采用其它的方式例如喷涂电镀的方式形成。
本发明的具体实施方式还提供一种涂覆制品，所述涂覆制品的至少部分表面具有如上所述的复合涂层。
本发明具体实施方式的涂覆制品，在一些具体实施方式中，所述制品为触控面板，例如包括手机、平板、车载、电视或LED等等的触控面板，在一些具体实施方式中，所述制品为电器制品，建筑制品或者任何对透明性、耐划痕性或耐磨性有要求的制品。
本发明具体实施方式的涂覆制品，在一些具体实施方式中，所述涂覆制品在涂覆前后的色差差值在0.5以下，在一些具体实施方式中，所述涂覆制品在涂覆前后的色差差值在0.4以下，在一些具体实施方式中，所述涂覆制品在涂覆前后的色差差值在0.3以下。
本发明具体实施方式的涂覆制品，具有优异的耐磨性，在一些具体实施方式中，所述制品的涂覆表面基材为玻璃，根据钢丝绒测试，用10N载荷经受6000次往复循环之后，速度40cycle/min，测试方向和钢丝绒的纤维方向相同，测试行程40mm，观察水滴角在100°以上，在一些具体实施方式中，所述制品的涂覆表面基材为玻璃，根据钢丝绒测试，用10N载荷经受7000次往复循环之后，速度40cycle/min，测试方向和钢丝绒的纤维方向相同，测试行程40mm，观察水滴角在100°以上，在一些具体实施方式中，所述制品的涂 覆表面基材为玻璃，根据钢丝绒测试，用10N载荷经受8000次往复循环之后，速度40cycle/min，测试方向和钢丝绒的纤维方向相同，测试行程40mm，观察水滴角在100°以上，在一些具体方式中，所述制品的涂覆表面基材为塑料，根据钢丝绒测试，用1N载荷经受800次往复循环之后，速度40cycle/min，测试方向和钢丝绒的纤维方向相同，测试行程40mm，观察水滴角在100°以上，在一些具体方式中，所述制品的涂覆表面基材为塑料，根据钢丝绒测试，用1N载荷经受900次往复循环之后，速度40cycle/min，测试方向和钢丝绒的纤维方向相同，测试行程40mm，观察水滴角在100°以上，在一些具体方式中，所述制品的涂覆表面基材为塑料，根据钢丝绒测试，用1N载荷经受1000次往复循环之后，速度40cycle/min，测试方向和钢丝绒的纤维方向相同，测试行程40mm，观察水滴角在100°以上。
以下通过具体实施例对本发明做进一步说明。
实施例
测试方法说明
涂层水滴角：根据GB/T 30447-2013标准进行测试。
涂层透光率及色差：根据GB11186.3-1989标准进行计算，使用KONICA分光谱仪CM-5，光源选择C光源进行检测，测试结果中ΔE表示色差，T表示透光率；L、a、b表示Lab颜色模型中的三个颜色通道，L表示亮度，a表示红绿，b表示黄蓝。
耐磨摩性能测试：采用Taber5900往复摩擦机，Bonstar#0000钢丝绒，玻璃基板使用10N载荷/塑料基板采用1N载荷，速度40cycle/min，测试方向和钢丝绒的纤维方向相同，测试行程40mm，观察水滴角小于100°的次数。
实施例1
将玻璃触控面板表面用干燥氮气吹扫干净，并放入等离子体反应器的真空腔室内，通过真空泵组将腔室内杂气排出，当真空压力小于0.05mT时，通入100sccm氩气，压力控制在30mT，打开偏压电源，馈入-400V电压，轰击清洗基材5min。随后关闭电源和气源，同时打开水浴控制水浴温度为26℃，该温度下，四甲基硅烷单体气体压力值控制在0.001MPa到0.003MPa之间， 调节气体流量阀，控制四甲基硅烷单体的流量为40sccm，氩气流量为100sccm，甲烷流量为80sccm，通入气体混合器混合后通入等离子体反应器，等离子体反应器的腔内压力控制在30mT，打开偏压电源，电压输入-300V，涂层时间10min，镀制获得一层20nm高透明高硬度DLC涂层，然后依次关闭电源、气源和泵组，打开等离子反应器的腔室门取出所述玻璃触控面板。
将上述DLC涂层完成后的玻璃触控面板放入AF蒸发腔室内，将真空抽到3.0×10-3Pa，通入UD509AF液，蒸发中电流12A，时间800s，蒸镀一层10nm的AF涂层，然后取出玻璃触控面板。
对上述依次沉积了DLC涂层与AF涂层的玻璃触控面板进行透光率、色差以及耐磨性能测试，结果列入下表1中。
实施例2
将实施例1中的玻璃触控面板改为PC触控面板，将基材清洗步骤中通入的100sccm氩气改为100sccm氧气，清洗时间延长至20min，其他工艺步骤不变，对依次沉积了DLC涂层与AF涂层的PC触控面板进行透光率、色差以及耐磨性能测试，结果列入下表1中。
实施例3
将实施例1中的玻璃触控面板改为PMMA触控面板，刻蚀清洗时间缩短至2min，其他工艺步骤不变，对依次沉积了DLC涂层与AF涂层的PMMA触控面板进行透光率、色差以及耐磨性能测试，结果列入下表1中。
实施例4
将实施例1中水浴温度设为10℃，四甲基硅烷单体换成三甲基硅烷单体，其他工艺步骤参数保持不变，对依次沉积了DLC涂层与AF涂层的玻璃触控面板进行透光率、色差以及耐磨性能测试，结果列入下表1中。
对比例1
将玻璃触控面板表面用干燥氮气吹扫干净，并放入等离子体反应器的真空腔室内，通过真空泵组将腔室内杂气排出，当真空压力小于0.05mT时，通入100sccm氩气，压力控制在30mT，打开偏压电源，馈入-400V电压，轰击 清洗基材5min取出，采用常规的喷涂方式在表面喷涂一层20nm二氧化硅层和10nm的UD509AF层。对涂层后的所述玻璃触控面板进行透光率、色差以及耐磨性能测试，结果列入下表1中。
对比例2
将玻璃触控面板表面用干燥氮气吹扫干净，并放入等离子体反应器的真空腔室内，通过真空泵组将腔室内杂气排出，当真空压力小于0.05mT时，通入100sccm氩气，压力控制在30mT，打开偏压电源，馈入-400V电压，轰击清洗基材5min取出，放入蒸发腔室内，首先将真空底压抽到4.0×10-3Pa以下，然后将装有二氧化硅的蒸发舟电流设置为30A，时间120s，蒸镀一层20nm的二氧化硅层，然后将真空抽到3.0×10-3Pa，通入UD509AF液至另一个蒸发舟中，蒸发舟电流12A，时间800s，蒸镀一层10nm的AF涂层，然后取出玻璃触控面板。对涂层后的所述玻璃触控面板进行透光率、色差以及耐磨性能测试，结果列入下表1中。
对比例3
将实施例1中的四甲基硅烷单体的流量设为零，延长镀膜时间至15min，其他工艺步骤参数保持不变，镀制获得一层20nmDLC涂层，然后同样的工艺条件制备10nm的AF涂层。对依次沉积了DLC涂层与AF涂层的玻璃触控面板进行透光率、色差以及耐磨性能测试，结果列入下表1中。
对比例4
对玻璃触控面板只进行干燥氮气吹扫干净，不进行涂层，对其进行透光率测试，结果列入下表1中。
对比例5
对PC触控面板只进行干燥氮气吹扫干净，不进行涂层，对其进行透光率测试，结果列入下表1中。
对比例6
对PMMA触控面板只进行干燥氮气吹扫干净，不进行涂层，对其进行透光率测试，结果列入下表1中。
表1实施例1-4与对比例1-6性能测试结果
根据上表1的结果，实施例1、实施例4涂层后的玻璃触控面板与对比例4未涂层的玻璃触控面板具有基本一致的透光率，实施例2涂层后的PC触控面板与对比例5未涂层的PC触控面板具有基本一致的透光率，实施例3涂层后的PMMA触控面板与对比例6未涂层的PMMA触控面板具有基本一致的透光率，表明本发明的DLC涂层及复合涂层具有优异的透光率；实施例1的耐摩擦次数远高于对比例1和对比例2的耐摩擦次数，表明本发明复合涂层相比于对比例1和对比例2的复合涂层具有更有优异的耐刮擦性能；与实施例1相比，对比例3中的DLC涂层中未通入四甲基硅烷单体进行Si掺杂，其透光率明显降低，色差显著提高，耐磨次数急剧降低，表明本发明的所述DLC涂层沉积AF涂层所获得的复合涂层具有低色差、高透明以及更加耐刮擦的特性。
虽然本发明披露如上，但本发明并非限定于此。任何本领域技术人员，在不脱离本发明的精神和范围内，均可作各种更动与修改，因此本发明的保护范围应当以权利要求所限定的范围为准。

Claims (24)

  1. 一种DLC涂层，其特征在于，所述DLC涂层为由Cx1Hy1的碳氢单体和Cx2Hy2Siz的硅烷单体通过PECVD方法沉积形成，其中，x1为1到10的整数，y1为2到22的整数，x2为0到32的整数，y2为4到68的整数，z为1到4的整数。
  2. 根据权利要求1所述的DLC涂层，其特征在于，常压下所述碳氢单体和硅烷单体的沸点在100℃以下。
  3. 根据权利要求2所述的DLC涂层，其特征在于，所述碳氢单体为甲烷、乙炔、苯或乙烯。
  4. 根据权利要求2所述的DLC涂层，其特征在于，所述硅烷单体为硅烷、甲基硅烷、二甲基硅烷、三甲基硅烷、四甲基硅烷、乙基硅烷或二乙基硅烷。
  5. 根据权利要求1所述的DLC涂层，其特征在于，所述碳氢单体与硅烷单体的摩尔比在60:40～95:5。
  6. 根据权利要求1所述的DLC涂层，其特征在于，所述DLC涂层的厚度为5-100nm。
  7. 一种权利要求1-6任意一项所述DLC涂层的制备装置，其特征在于，所述装置包括：
    等离子体反应器，用于通过PECVD方法沉积形成DLC涂层；
    单体气化控制装置，用于将常温下为液体的碳氢单体加热气化或者控制硅烷单体的气化状态；
    气体流量计，用于计量控制气化后的单体流量；
    保温装置，用于对单体流动线路保温，以保证所述单体气化控制装置中的气化单体稳定通入所述等离子体反应器。
  8. 根据权利要求7的所述DLC涂层的制备装置，其特征在于，所述装置还包 括设置于单体气化控制装置与气体流量计之间的压力表，可根据所述压力表读数控制单体气化控制装置的温度。
  9. 一种权利要求1-6任意一项所述DLC涂层的制备方法，其特征在于，包括以下步骤：
    提供基材，将基材置于等离子体反应器中；
    将所述碳氢单体和硅烷单体的气体计量通入所述等离子体反应器中，开启偏压电源，采用PECVD方法在所述基材上沉积DLC涂层。
  10. 根据权利要求9所述的DLC涂层制备方法，其特征在于，所述碳氢单体和硅烷单体分别以气体的形式由气体流量计计量通入。
  11. 根据权利要求10所述的DLC涂层制备方法，其特征在于，控制所述硅烷单体温度，将所述硅烷单体气体的压力控制在0.001MPa到0.003MPa之间。
  12. 根据权利要求10所述的DLC涂层制备方法，其特征在于，所述碳氢单体的流量为10-200sccm，硅烷单体的流量为5-100sccm。
  13. 根据权利要求10所述的DLC涂层制备方法，其特征在于，通入单体气体的同时通入惰性气体，所述惰性气体的流量为20-200sccm。
  14. 根据权利要求10所述的DLC涂层制备方法，其特征在于，等离子体反应器中的压力为15-100mT，偏压电压输入为-200至-800V，涂层沉积时间为2-30min。
  15. 一种复合涂层，其特征在于，所述复合涂层包括权利要求1-6任意一项所述DLC涂层以及形成于所述DLC涂层上的AF涂层。
  16. 根据权利要求15所述的复合涂层，其特征在于，所述AF涂层的原材料包括全氟聚醚聚合物。
  17. 根据权利要求16所述的复合涂层，其特征在于，所述全氟聚醚聚合物为全氟聚醚硅烷或全氟聚醚烷氧基硅烷。
  18. 根据权利要求15所述的复合涂层，其特征在于，所述AF涂层的厚度为5-20nm。
  19. 根据权利要求15所述的复合涂层，其特征在于，通过真空蒸镀的方法沉积形成所述AF涂层。
  20. 一种涂覆制品，其特征在于，所述涂覆制品的至少部分表面具有权利要求15-19中任意一项所述的复合涂层。
  21. 根据权利要求20所述的涂覆制品，其特征在于，所述制品为触控面板。
  22. 根据权利要求20所述的涂覆制品，其特征在于，所述涂覆制品在涂覆前后的色差差值在0.5以下。
  23. 根据权利要求20所述的涂覆制品，其特征在于，所述制品的涂覆表面基材为玻璃，根据钢丝绒测试，用10N载荷经受6000次往复循环之后，速度40cycle/min，测试方向和钢丝绒的纤维方向相同，测试行程40mm，观察水滴角在100°以上。
  24. 根据权利要求20所述的涂覆制品，其特征在于，所述制品的涂覆表面基材为塑料，根据钢丝绒测试，用1N载荷经受800次往复循环之后，速度40cycle/min，测试方向和钢丝绒的纤维方向相同，测试行程40mm，观察水滴角在100°以上。
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