WO2022247633A1 - 一种等离子体聚合涂层、制备方法及器件 - Google Patents

一种等离子体聚合涂层、制备方法及器件 Download PDF

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Publication number
WO2022247633A1
WO2022247633A1 PCT/CN2022/092128 CN2022092128W WO2022247633A1 WO 2022247633 A1 WO2022247633 A1 WO 2022247633A1 CN 2022092128 W CN2022092128 W CN 2022092128W WO 2022247633 A1 WO2022247633 A1 WO 2022247633A1
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plasma
polymerized coating
monomer
group
plasma polymerized
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French (fr)
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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 EP22810360.2A priority Critical patent/EP4350031A4/en
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    • 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
    • B05D1/60—Deposition of organic layers from vapour phase
    • 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
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C23C16/515—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 pulsed discharges
    • 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
    • B05D2506/00—Halogenated polymers
    • B05D2506/10—Fluorinated polymers
    • 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
    • B05D2518/00—Other type of polymers
    • B05D2518/10—Silicon-containing polymers
    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0493—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases using vacuum

Definitions

  • the invention belongs to the field of plasma chemistry, and in particular relates to a plasma polymerized coating, a preparation method and a device.
  • PECVD plasma enhanced chemistry
  • Nano water-resistant protective coating the protective coating is uniform, the coating preparation temperature is low, the coating thickness is thin, the stress is small, there is almost no damage to the surface of the substrate and almost no influence on the performance of the substrate.
  • Forming a waterproof protective coating on the surface of a substrate by PECVD has been used more and more.
  • the research on the waterproof protective coating mainly focuses on how to improve its waterproof performance and how to improve the bonding force between the coating and the substrate.
  • the coating is thin, and when it is scratched or rubbed by external force, it is easily damaged and affects its protective performance. How to improve the wear resistance of its coating itself has not yet been seen.
  • the specific embodiment of the present invention provides a plasma polymerized coating, a preparation method and a device for improving wear resistance, and the specific scheme is as follows:
  • the reactive monomer includes a monomer having a structure shown in formula (1),
  • R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen atom, halogen atom, C 1 -C 20 substituted or unsubstituted hydrocarbon group, C 1 -C 20 substituted or Unsubstituted alkoxy or C 4 -C 20 aryl;
  • R 1 , R 2 , R 3 and R 4 contains an epoxy group or is a C 4 -C 20 aromatic group.
  • the R 1 , R 2 , R 3 and R 4 are independently selected from a hydrogen atom, a halogen atom, a C 1 -C 20 hydrocarbon group, a C 1 -C 20 substituent with an epoxy structure Hydrocarbyl, C 1 -C 20 alkoxy, C 1 -C 20 alkoxy with epoxy substituent or C 6 -C 20 aryl.
  • the R 1 , R 2 , R 3 and R 4 are independently selected from a hydrogen atom, a halogen atom, a C 1 -C 4 alkane group, a C 1 -C 4 alkane oxy group, a C 1 -C 4 alkenyl, C 1 -C 4 alkenyloxy or C 6 -C 20 aryl; wherein at least one of R 1 , R 2 , R 3 and R 4 is C 6 -C 20 aromatic base.
  • the aryl is phenyl
  • the monomer having the structure shown in formula (1) is selected from phenyltrichlorosilane, chlorodiphenylsilane, diphenyldichlorosilane, triphenylvinylsilane, diphenyldivinylsilane , one or more of diphenyldimethoxysilane or trimethoxyphenylsilane.
  • the R 1 , R 2 , R 3 and R 4 are independently selected from a hydrogen atom, a halogen atom, a C 1 -C 4 alkane group, a C 1 -C 4 alkane oxy group, a C 1 -C 4 alkenyl, C 1 -C 4 alkenyloxy, C 2 -C 10 epoxy alkoxyl or C 2 -C 10 epoxy alkyl; wherein R 1 , R 2 , R 3 and R At least one of 4 is a C 2 -C 10 epoxyalkoxyalkyl group or a C 2 -C 10 epoxyalkyl group.
  • the epoxy is cycloaliphatic epoxy.
  • the monomer having the structure shown in formula (1) is selected from 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane, 3-(2,3-epoxypropylene Oxy)propyltrimethoxysilane, ⁇ -(3,4-epoxycyclohexyl)-ethyltrimethoxysilane or 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane one or more of.
  • the reactive monomer further includes one or more of fluorocarbons, fluoroacrylates or fluorosilanes.
  • Z is a connecting part
  • R 5 , R 6 and R 7 are independently selected from a hydrogen atom, a halogen atom, a C 1 -C 10 hydrocarbon group or a C 1 -C 10 halogen atom substituted hydrocarbon group, and x is 1- An integer of 20.
  • the Z is a link, a C 1 -C 4 alkylene group or a C 1 -C 4 alkylene group with substituents, and x is more than 4.
  • R 5 , R 6 and R 7 are independently selected from a hydrogen atom or a methyl group.
  • the fluoroacrylate is selected from 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl methacrylate, 2-(perfluorodecyl)ethyl methacrylate , 2-(perfluorohexyl) ethyl methacrylate, 2-(perfluorododecyl) ethyl acrylate, 2-perfluorooctyl ethyl acrylate, 1H,1H,2H,2H-perfluoro One or more of octanol acrylate, 2-(perfluorobutyl) ethyl acrylate or (perfluorocyclohexyl) methacrylate.
  • the substrate is metal, plastic, fabric, glass, electrical components, optical instruments or electrical components.
  • the substrate is a glass screen.
  • a method for preparing any of the above plasma polymerized coatings comprising:
  • a substrate is provided, and the substrate is placed in a plasma reactor; the reactive monomer is vaporized into the plasma reactor, plasma is discharged, and a coating is formed on the surface of the substrate by plasma polymerization.
  • the plasma is pulsed plasma.
  • the pulsed plasma is generated by applying a pulse voltage discharge, wherein the pulse power is 10W-300W, the pulse duty ratio is 0.1%-80%, and the plasma discharge time is 100s-36000s.
  • the plasma polymerized coating according to the specific embodiment of the present invention is formed of a plasma polymerized coating containing an organosilane monomer having an aromatic group or an epoxy group, which can effectively improve the wear resistance of the plasma polymerized coating.
  • a plasma polymerized coating according to a particular embodiment of the invention said coating being formed by plasma reactive deposition of a substrate in contact with a reactive monomer
  • the reactive monomer has a monomer of the structure shown in formula (1),
  • R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen atom, halogen atom, C 1 -C 20 substituted or unsubstituted hydrocarbon group, C 1 -C 20 substituted or Unsubstituted alkoxy or C 4 -C 20 aryl;
  • R 1 , R 2 , R 3 and R 4 contains an epoxy group or is a C 4 -C 20 aromatic group.
  • the inventors of the present invention have found that, possibly due to the rigidity of the aryl aromatic ring, the high reactivity of the epoxy group is easy to form a network structure.
  • the plasma polymerized coating formed by the body can effectively improve the wear resistance of the plasma polymerized coating.
  • the hydrocarbon group can be an alkane group, an alkene group or an alkyne group, or an alicyclic hydrocarbon group or an aromatic hydrocarbon group
  • the alkoxy group can be an alkane group, an alkene group Or an alkyneoxy group, or an alicyclic hydrocarbon group or an aromatic group group.
  • the substituted substituents can be, for example, halogen atoms, epoxy groups, nitro groups, cyano groups, sulfonic acid groups, amino groups, carboxyl groups, hydroxyl groups, mercapto groups, hydrocarbon groups, hydrocarbon oxygen groups group or acyl group, etc., the substituent may be one or more than two.
  • the aromatic group is an aryl group or a heteroaryl group.
  • said R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen atoms, halogen atoms, C 1 -C 20 Hydrocarbyl, C 1 -C 20 hydrocarbon group with epoxy structure substituent, C 1 -C 20 alkoxyl group, C 1 -C 20 hydrocarbon group with epoxy structure substituent or C 6 -C 20 aryl.
  • said R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen atoms, halogen atoms, C 1 -C 4 Alkyl, C 1 -C 4 alkoxyl, C 1 -C 4 alkenyl, C 1 -C 4 alkenyloxy or C 6 -C 20 aryl; where R 1 , R 2 , R 3 and at least one of R 4 is a C 6 -C 20 aryl group.
  • the alkane group can be, for example, methyl, ethyl, propyl, butyl or isopropyl, etc.
  • the alkoxy group can be, for example, methoxy, ethoxy, propoxy, butoxy Or isopropoxy etc.
  • described alkene group can be ethenyl, propenyl or butenyl etc.
  • described alkene oxygen group can be 2-(allyloxy) for example
  • described aryl group can be phenyl for example , p-tolyl or biphenyl, etc.
  • the monomer having the structure shown in formula (1) is selected from phenyltrichlorosilane (CAS: 98-13-5), chlorodiphenylsilane (CAS: 1631-83-0), diphenyl Dichlorosilane (CAS: 80-10-4), triphenylvinylsilane (CAS: 18666-68-7), diphenyldivinylsilane (CAS: 17937-68-7), diphenyldiphenylsilane One or more of methoxysilane (CAS: 6843-66-9) or trimethoxyphenylsilane (CAS: 2996-92-1).
  • said R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen atoms, halogen atoms, C 1 -C 4 Alkyl group, C 1 -C 4 alkoxyl group, C 1 -C 4 alkenyl group, C 1 -C 4 alkenyloxy group, C 2 -C 10 epoxy alkoxyl group or C 2 -C 10 Epoxyalkyl group; wherein at least one of R 1 , R 2 , R 3 and R 4 is a C 2 -C 10 epoxyalkylene group or a C 2 -C 10 epoxyalkylene group.
  • the alkane group can be, for example, methyl, ethyl, propyl, butyl or isopropyl, etc.
  • the alkoxy group can be, for example, methoxy, ethoxy, propoxy, butoxy or isopropoxy, etc.
  • the alkene group can be vinyl, propenyl or butenyl, etc.
  • the alkene oxygen group can be, for example, 2-(allyloxy)
  • the epoxy alkoxy group for example, can be Is (2,3-epoxypropoxy)ethyl, (2,3-epoxypropoxy)propyl, (3,4-epoxybutoxy)ethyl or (3,4-epoxybutoxy) Propyl, etc.
  • the epoxy hydrocarbon group can be, for example, 2,3-epoxypropyl, 3,4-epoxyethyl, 3,4-epoxybutyl or 3,4-epoxycyclohexyl, etc.
  • the monomer having the structure shown in formula (1) is selected from 3-(2,3-glycidoxy)propylmethyldimethoxysilane (CAS: 65799-47-5), 3 -(2,3-Epoxypropoxy)propyltrimethoxysilane (CAS: 2530-83-8), ⁇ -(3,4-epoxycyclohexyl)-ethyltrimethoxysilane (CAS: 3388- 04-3) or one or more of 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane (CAS: 10217-34-2).
  • the epoxy is an alicyclic epoxy, such as 3,4-epoxycyclohexyl, which has a better effect of improving wear resistance.
  • the reactive monomers also include one or more fluorine-containing monomers in fluorocarbons, fluoroacrylates or fluorosilanes , in some specific embodiments, the structure of the fluoroacrylate is shown in formula (2),
  • Z is a connecting part
  • R 5 , R 6 and R 7 are independently selected from a hydrogen atom, a halogen atom, a C 1 -C 10 hydrocarbon group or a C 1 -C 10 halogen atom substituted hydrocarbon group, and x is 1- An integer of 20.
  • the Z is a linking part, which is used to connect the ester bond and the perfluorocarbon alkyl group.
  • the Z is a linking bond, C 1 -C 4 An alkylene group or a C 1 -C 4 alkylene group having substituents.
  • the alkylene group includes straight-chain alkylene groups, such as methylene, ethylene, propylene or butylene groups, or branched-chain alkylene groups, such as isopropylidene or isobutylene groups, etc.
  • the substituent includes, for example, a halogen atom, a hydroxyl group, a carboxyl group or an ester group and the like.
  • the reactive monomer includes both the fluoroacrylate monomer with the structure shown in formula (2) and the monomer with the structure shown in formula (1)
  • the reactive monomer includes both the fluoroacrylate monomer with the structure shown in formula (2) and the monomer with the structure shown in formula (1)
  • said x is more than 4, further more than 6, and said x is specifically for example 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, the The plasma polymerized coating can still maintain excellent water and oil repellency after repeated friction.
  • the fluoroacrylate is selected from 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl methacrylic acid Esters (CAS: 16083-81-1), 2-(perfluorodecyl)ethyl methacrylate (CAS: 2144-54-9), 2-(perfluorohexyl)ethyl methacrylate (CAS : 2144-53-8), 2-(perfluorododecyl) ethyl acrylate (CAS: 34395-24-9), 2-perfluorooctyl ethyl acrylate (CAS: 27905-45-9) , 1H,1H,2H,2H-perfluorooctyl acrylate (CAS: 17527-29-6), 2-(perfluorobutyl) ethyl acrylate (CAS: 52591-27-2) or (perfluoro One or
  • the substrate is metal, specifically for example, iron, magnesium, aluminum, copper or alloys thereof, in other specific embodiments, the substrates mentioned above are various plastics, fabrics, glass, electrical components or optical instruments, etc.
  • the electrical component may be a printed circuit board (PCB), an electronic product or an electronic assembly semi-finished product, and the like.
  • PCB printed circuit board
  • the substrate is an electronic product, examples but not limited to mobile phones, tablet computers, keyboards, e-readers, wearable devices, displays and the like.
  • the substrate may also be any suitable electrical component of an electrical assembly, specifically, the electrical component may be a resistor, capacitor, transistor, diode, amplifier, relay, transformer, battery, fuse, integrated circuit, switch , LED, LED display, piezoelectric element, optoelectronic component or antenna or oscillator, etc.
  • the electrical component may be a resistor, capacitor, transistor, diode, amplifier, relay, transformer, battery, fuse, integrated circuit, switch , LED, LED display, piezoelectric element, optoelectronic component or antenna or oscillator, etc.
  • the substrate is a glass screen, especially a mobile phone screen.
  • smart phones have been popularized.
  • many mobile phones Manufacturers will choose glass coated with anti-fingerprint film as the mobile phone screen.
  • the screen As far as the screen is concerned, there is no anti-fingerprint process on the screen, which greatly reduces the waterproof and oil-proof performance of the mobile phone during use.
  • the plasma polymerized coating according to the specific embodiment of the present invention has easier coating preparation, uniform coating, thin thickness, small stress, almost no damage to the substrate surface and almost no influence on the performance of the substrate, and has excellent wear resistance at the same time Performance, especially suitable as a protective coating for glass screens such as mobile phones.
  • the plasma polymerized coating of the specific embodiment of the present invention contacts the monomer of the structure shown in formula (1) and the monomer of described fluoroacrylate by substrate contact Formed by plasma deposition.
  • the molar ratio of the monomer of the structure represented by the formula (1) to the monomer of the fluoroacrylate is between 3:10 and 10:3, specifically for example Can be 3:10, 4:10, 5:10, 6:10, 7:10, 8:10, 9:10, 10:10, 10:9, 10:8, 10:7, 10:6, 10:5, 10:4 or 10:3 and so on.
  • the coating may be formed by the plasma of the monomer having the structure represented by the formula (1) and other monomers in contact with the substrate.
  • the specific embodiment of the present invention also provides a method for preparing any one of the above plasma polymerized coatings, including:
  • a substrate is provided, and the substrate is placed in a plasma reactor; the monomer is vaporized into the plasma reactor, plasma is discharged, and a coating is formed on the surface of the substrate by plasma polymerization.
  • the preparation method of the plasma polymerized coating according to the specific embodiment of the present invention provides a method for increasing the wear resistance of the plasma polymerized coating.
  • the preparation method of the plasma polymerized coating according to the specific embodiment of the present invention is as described above for the monomer and the substrate.
  • the preparation method of the plasma polymerized coating of the specific embodiment of the present invention for some substrates, such as mobile phone screens or circuit boards, in order to further enhance the bonding force between the plasma coating and the substrate, in some specific embodiments , before coating, the substrate is pretreated with continuous plasma, the specific pretreatment method is, for example, in an inert gas atmosphere, the plasma discharge power is 20-500W, the discharge method is continuous, and the discharge time is continuous 1 to 60 minutes, or by means of heat, oxygen or high-energy radiation, etc.
  • the plasma is a plasma excited by a continuous wave
  • the plasma is
  • the monomer flow rate is 50-500 ⁇ L/min, for example, it can be 100 ⁇ L/min, 200 ⁇ L/min, 300 ⁇ L/min or 400 ⁇ L/min, etc.
  • the temperature in the cavity is controlled at 20°C-80°C °C, for example, it can be 20 °C, 30 °C, 40 °C, 50 °C, 60 °C, 70 °C or 80 °C, etc.
  • the vaporization temperature of the monomer is 50 °C-180 °C, for example, it can be 50 °C, 60 °C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C
  • Specific for examples can be 100S, 500S, 1000S, 1800S, 2000S, 1000S, 2000S, 3000S, 4000S, 5000S, 6000S, 7000S, 7200S, 10800S, 14400S, 21600S, 25200S, 28800S, 32400S or 36000S or 36000S and many more.
  • the plasma discharge mode can be various existing discharge modes, specifically for example, electrodeless discharge (such as radio frequency inductively coupled discharge , microwave discharge), single-electrode discharge (such as corona discharge, plasma jet formed by unipolar discharge), double-electrode discharge (such as dielectric barrier discharge, exposed electrode radio frequency glow discharge) and multi-electrode discharge (such as floating electrode as the discharge of the third electrode).
  • electrodeless discharge such as radio frequency inductively coupled discharge , microwave discharge
  • single-electrode discharge such as corona discharge, plasma jet formed by unipolar discharge
  • double-electrode discharge such as dielectric barrier discharge, exposed electrode radio frequency glow discharge
  • multi-electrode discharge such as floating electrode as the discharge of the third electrode.
  • Specific embodiments of the present invention also provide a device, at least part of the surface of the device has any one of the above-mentioned plasma polymerized coatings, in some specific embodiments, part or all of the surface of the device is deposited with The aforementioned plasma polymerized coating.
  • the mobile phone screen Place the mobile phone screen in the plasma chamber, continuously evacuate the chamber to 5 mTorr, inject helium gas with a flow rate of 40 sccm, and turn on the plasma discharge with a pulse power of 180W and a duty cycle of 1.5%; the monomer ⁇ - (3,4 epoxycyclohexyl)-ethyltrimethoxysilane and monomer 2-perfluorooctyl ethyl acrylate are vaporized at a vaporization temperature of 180°C and then introduced into the cavity for plasma chemical vapor deposition, wherein The flow rate of the monomer ⁇ -(3,4 epoxycyclohexyl)-ethyltrimethoxysilane is 75 ⁇ L/min, and the flow rate of the monomer 2-perfluorooctyl ethyl acrylate is 75 ⁇ L/min; the reaction time is 5400s; after the discharge Introduce compressed air to restore the cavity to normal pressure, open the cavity, and take out the mobile phone screen
  • the mobile phone screen Place the mobile phone screen in the plasma chamber, continuously evacuate the chamber to 5 millitorr, inject helium gas with a flow rate of 40sccm, and turn on the plasma discharge with a pulse power of 180W and a duty cycle of 1.5%; the monomer 3- (2,3-Glycidoxy)propyltrimethoxysilane and monomer 2-perfluorooctyl ethyl acrylate are vaporized at a vaporization temperature of 180°C and then introduced into the cavity for plasma chemical vapor deposition, wherein The flow rate of the monomer 3-(2,3-glycidoxy)propyltrimethoxysilane is 75 ⁇ L/min, the flow rate of the monomer 2-perfluorooctyl ethyl acrylate is 75 ⁇ L/min; the reaction time is 5400s; after the discharge Introduce compressed air to restore the cavity to normal pressure, open the cavity, and take out the mobile phone screen.
  • the flow rate of the monomer 2-perfluorooctyl ethyl acrylate is 75 ⁇ L/min; the reaction time is 5400s; after the discharge, the compressed air is introduced to restore the chamber to normal pressure, the chamber is opened, and the mobile phone screen is taken out.
  • the plasma polymerized coating comprising organosilicon monomer ⁇ -(3,4 epoxycyclohexyl)-ethyltrimethoxysilane with alicyclic epoxy group has the best Excellent wear resistance, after 1000 times of friction, the water drop angle remains at 108°, and the n-hexadecane oil drop angle remains at 72°.
  • the plasma polymerized coating containing the organosilicon monomer 3-(2,3-glycidoxy)propyltrimethoxysilane with a chain hydrocarbon epoxy group has good wear resistance, and the friction is 1000
  • the drop angle of water remained at 102°
  • the drop angle of n-hexadecane oil remained at 65°, but the effect was slightly worse than that of scheme one.
  • the wear resistance of the plasma polymerized coating is poor, and the water drop angle remains only 1000 after 1000 frictions without silicone monomer or with non-epoxy silicone monomer tetramethoxysilane. are 60° and 67°
  • the n-hexadecane oil drop angle remains only 52° and 56°.
  • the mobile phone screen placed in the plasma chamber, continuously evacuate the chamber to 5 mTorr, inject helium gas with a flow rate of 40 sccm, and turn on the plasma discharge with a pulse power of 180W and a duty cycle of 1%; the monomer phenyl Trimethoxysilane and monomer 1H,1H,2H,2H-perfluorooctyl acrylate are vaporized at a vaporization temperature of 145°C and then introduced into the chamber for plasma chemical vapor deposition, wherein the monomer phenyltrimethoxy
  • the flow rate of silane is 80 ⁇ L/min
  • the flow rate of monomer 1H, 1H, 2H, 2H-perfluorooctyl acrylate is 80 ⁇ L/min
  • the reaction time is 6000 s
  • after the discharge, the compressed air is introduced to restore the chamber to normal pressure and open the chamber Body, take out the phone screen.
  • Place another mobile phone screen in the plasma chamber continuously evacuate the chamber to 5 mTorr, inject helium gas with a flow rate of 40 sccm, and turn on the plasma discharge with a pulse power of 180W and a duty cycle of 1%.
  • 1H, 1H, 2H, 2H-perfluorooctyl acrylate vaporized at a vaporization temperature of 145°C and then introduced into the chamber for plasma chemical vapor deposition, in which the monomer 1H, 1H, 2H, 2H-perfluorooctyl
  • the flow rate of acrylate is 160 ⁇ L/min; the reaction time is 6000s; after the discharge, the compressed air is introduced to restore the normal pressure of the cavity, the cavity is opened, and the mobile phone screen is taken out.
  • the monomer tetramethoxysilane flow The flow rate of the monomer 1H, 1H, 2H, 2H-perfluorooctyl acrylate is 80 ⁇ L/min; the reaction time is 6000s; after the discharge, the compressed air is introduced to restore the chamber to normal pressure, and the chamber is opened. Take out the phone screen.
  • the plasma polymerized coating of the body has been worn directly after 500 frictions, and the water drop angle of the plasma polymerized coating containing the organosilicon monomer tetramethoxysilane without aryl group remains only 55° after 500 times of friction, positive sixteen The paraffin oil drop angle remains only 36°.
  • the monomer 1H, 1H, 2H, 2H-perfluorooctyl acrylate flow rate is 60 ⁇ L/min; the reaction time is 5000s; after the discharge, the compressed air is introduced to restore the chamber to normal pressure, open the chamber, and take out the mobile phone screen .
  • Place another mobile phone screen in the plasma chamber continuously evacuate the chamber to 5 mTorr, inject helium gas with a flow rate of 40 sccm, and turn on the plasma discharge with a pulse power of 180W and a duty cycle of 1.5%; 1H, 1H, 2H, 2H-perfluorooctyl acrylate, vaporized at a vaporization temperature of 180°C and then introduced into the chamber for plasma chemical vapor deposition, in which the monomer 1H, 1H, 2H, 2H-perfluorooctanol
  • the flow rate of acrylate is 150 ⁇ L/min; the reaction time is 5000s; after the discharge, the compressed air is introduced to restore the normal pressure of the cavity, the cavity is opened, and the mobile phone screen is taken out.
  • the monomer ⁇ -(3,4 epoxycyclohexyl)-ethyltrimethoxysilane and the monomer 2-perfluorooctyl ethyl acrylate are vaporized at a vaporization temperature of 180°C and then introduced into the chamber for Plasma chemical vapor deposition, wherein the flow rate of the monomer ⁇ -(3,4 epoxycyclohexyl)-ethyltrimethoxysilane is 100 ⁇ L/min, and the flow rate of the monomer 2-perfluorooctyl ethyl acrylate is 100 ⁇ L/min;
  • the reaction time is 3600s; after the discharge, the compressed air is introduced to restore the chamber to normal pressure, the chamber is
  • the monomer 2-perfluorooctyl ethyl acrylate is vaporized at a vaporization temperature of 180°C and then introduced into the chamber for plasma chemical vapor deposition, wherein the monomer 2-perfluorooctyl ethyl acrylate flow
  • the reaction time is 200 ⁇ L/min; the reaction time is 3600s; after the discharge, the compressed air is introduced to restore the chamber to normal pressure, the chamber is opened, and the Fe sheet is taken out.
  • the wear resistance test of the Fe sheets of Scheme 1 and Scheme 2 was carried out on a wear-resistant testing machine, the friction material was dust-free cloth, the load was 100g, and the rotational speed was 50r/min. Record the water drop angle and n-hexadecane oil drop angle every 100 times of friction.

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Abstract

本发明具体实施方式提供一种等离子体聚合涂层，所述等离子体聚合涂层由基材接触包含具有芳香基或环氧基的有机硅烷单体的等离子体沉积形成，由包含该单体的等离子体沉积形成的涂层，可有效提升其涂层的耐磨性。

Description

一种等离子体聚合涂层、制备方法及器件
本申请要求于2021年5月26日提交中国专利局、申请号为202110580670.5、发明名称为“一种等离子体聚合涂层、制备方法及器件”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
本发明属于等离子化学领域，具体涉及一种等离子体聚合涂层、制备方法及器件。
背景技术
等离子体增强化学的工艺(PECVD)借助微波或射频等使含有薄膜成分的气体电离，在局部形成等离子体，而等离子体化学活性很强，很容易发生反应，可在基材上沉积出所期望的纳米抗水保护涂层，该保护涂层均匀，涂层制备温度低，涂层厚度薄、应力小，对基材表面几乎没有损伤和基材性能几乎没有影响。
通过PECVD在基材表面形成防水保护涂层已被越来越多的应用，目前对于所述防水保护涂层的研究主要集中在如何提高其防水性能，以及如何提高涂层与基材的结合力，而对于所述通过PECVD形成的防水保护涂层，涂层薄，当受到外力刮擦或摩擦时，容易受到损伤而影响其防护性能，对于如何提高其涂层自身的耐磨性能暂未见相关报道。
发明内容
针对以上现有技术中的问题，本发明的具体实施方式提供一种提升耐磨性的等离子体聚合涂层、制备方法及器件，具体方案如下：
一种等离子体聚合涂层，所述涂层由基材接触反应性单体的等离子体反应沉积形成，
其中，所述反应性单体包括具有式(1)所示结构的单体，
Figure PCTCN2022092128-appb-000001
式(1)中，R 1、R 2、R 3和R 4分别独立的选自于氢原子、卤素原子、C 1-C 20的取代或未取代的烃基、C 1-C 20的取代或未取代的烃氧基或C 4-C 20的芳香基；
其中R 1、R 2、R 3和R 4中的至少一个包含环氧基或为C 4-C 20的芳香基。
可选的，所述R 1、R 2、R 3和R 4分别独立的选自于氢原子、卤素原子、C 1-C 20的烃基、C 1-C 20的带有环氧结构取代基的烃基、C 1-C 20的烃氧基、C 1-C 20的带有环氧结构取代基的烃氧基或C 6-C 20的芳基。
可选的，所述R 1、R 2、R 3和R 4分别独立的选自于氢原子、卤素原子、C 1-C 4的烷烃基、C 1-C 4的烷烃氧基、C 1-C 4的烯烃基、C 1-C 4的烯烃氧基或C 6-C 20的芳基；其中R 1、R 2、R 3和R 4中的至少一个为C 6-C 20的芳基。
可选的，所述芳基为苯基。
可选的，具有式(1)所示结构的单体选自于苯基三氯硅烷、氯二苯基硅烷、二苯二氯硅烷、三苯基乙烯基硅烷、二苯基二乙烯基硅烷、二苯基二甲氧基硅烷或三甲氧基苯基硅烷中的一种或几种。
可选的，所述R 1、R 2、R 3和R 4分别独立的选自于氢原子、卤素原子、C 1-C 4的烷烃基、C 1-C 4的烷烃氧基、C 1-C 4的烯烃基、C 1-C 4的烯烃氧基、C 2-C 10的环氧烃氧烃基或C 2-C 10的环氧烃基；其中R 1、R 2、R 3和R 4中的至少一个为C 2-C 10的环氧烃氧烃基或C 2-C 10的环氧烃基。
可选的，所述环氧为脂环族环氧。
可选的，具有式(1)所示结构的单体选自于3-(2,3-环氧丙氧)丙基甲基二甲氧基硅烷、3-(2,3-环氧丙氧)丙基三甲氧基硅烷、β-(3、4环氧环己基)-乙基三甲氧基硅烷或2-(3,4-环氧环己烷基)乙基三乙氧基硅烷中的一种或几种。
可选的，所述反应性单体还包括氟代烃、氟代丙烯酸酯或氟代硅烷中的一种或几种。
可选的，所述氟代丙烯酸酯的结构如式(2)所示，
Figure PCTCN2022092128-appb-000002
其中，Z为连接部分，R 5、R 6和R 7分别独立的选自于氢原子、卤素原子、C 1-C 10的烃基或C 1-C 10的卤原子取代烃基，x为1-20的整数。
可选的，所述Z为连接键、C 1-C 4的亚烷基或具有取代基的C 1-C 4的亚烷基，x在4以上。
可选的，所述R 5、R 6和R 7分别独立的选自于氢原子或甲基。
可选的，所述氟代丙烯酸酯选自于3-(全氟-5-甲基己基)-2-羟基丙基甲基丙烯酸酯、2-(全氟癸基)乙基甲基丙烯酸酯、2-(全氟己基)乙基甲基丙烯酸酯、2-(全氟十二烷基)乙基丙烯酸酯、2-全氟辛基丙烯酸乙酯、1H,1H,2H,2H-全氟辛醇丙烯酸酯、2-(全氟丁基)乙基丙烯酸酯或(全氟环己基)甲基丙烯酸酯中的一种或几种。
可选的，所述基材为金属、塑料、织物、玻璃、电气组件、光学仪器或电气部件。
可选的，所述基材为玻璃屏。
一种任意以上所述的等离子体聚合涂层的制备方法，包括：
提供基材，将基材置于等离子体反应器中；将所述反应性单体汽化进入等离子体反应器，等离子体放电，在所述基材的表面等离子体聚合形成涂层。
可选的，所述等离子体为脉冲等离子体。
可选的，所述脉冲等离子体通过施加脉冲电压放电产生，其中，脉冲功率为10W～300W，脉冲占空比为0.1％～80％，等离子放电时间为100s～36000s。
一种器件，所述器件的至少部分表面具有任意以上所述的等离子体聚合涂层。
本发明具体实施方式的等离子体聚合涂层，由包含具有芳香基或环氧基的有机硅烷单体形成的等离子体聚合涂层，可有效提升等离子体聚合涂层的耐磨性。
具体实施方式
本发明具体实施方式的等离子体聚合涂层，所述涂层由基材接触反应性单体的等离子体反应沉积形成，
其中，所述反应性单体具有式(1)所示结构的单体，
Figure PCTCN2022092128-appb-000003
式(1)中，R 1、R 2、R 3和R 4分别独立的选自于氢原子、卤素原子、C 1-C 20的取代或未取代的烃基、C 1-C 20的取代或未取代的烃氧基或C 4-C 20的芳香基；
其中R 1、R 2、R 3和R 4中的至少一个包含环氧基或为C 4-C 20的芳香基。
本发明的发明人研究发现，可能由于芳基芳香环的刚性作用，环氧基的高反应活性易于形成网络结构，由包含式(1)所示的具有芳基或环氧基的有机硅烷单体形成的等离子体聚合涂层，可有效提升等离子体聚合涂层的耐磨性。
本发明具体实施方式的等离子体聚合涂层，所述烃基可以是烷烃基、烯烃基或炔烃基，也可以是脂环烃基或芳烃基，所述烃氧基可以是烷烃氧基、烯烃氧基或炔烃氧基，也可以是脂环烃氧基或芳烃氧基。
本发明具体实施方式的等离子体聚合涂层，所述取代的取代基例如可以是卤素原子、环氧基、硝基、氰基、磺酸基、氨基、羧基、羟基、巯基、烃基、烃氧基或酰基等等，所述取代基可以是一个或两个以上。
本发明具体实施方式的等离子体聚合涂层，所述芳香基为芳基或杂芳基。
本发明具体实施方式的等离子体聚合涂层，在一些具体实施方式中，所述R 1、R 2、R 3和R 4分别独立的选自于氢原子、卤素原子、C 1-C 20的烃基、C 1-C 20 的带有环氧结构取代基的烃基、C 1-C 20的烃氧基、C 1-C 20的带有环氧结构取代基的烃氧基或C 6-C 20的芳基。
本发明具体实施方式的等离子体聚合涂层，在一些具体实施方式中，所述R 1、R 2、R 3和R 4分别独立的选自于氢原子、卤素原子、C 1-C 4的烷烃基、C 1-C 4的烷烃氧基、C 1-C 4的烯烃基、C 1-C 4的烯烃氧基或C 6-C 20的芳基；其中R 1、R 2、R 3和R 4中的至少一个为C 6-C 20的芳基。作为举例，所述烷烃基例如可以是甲基、乙基、丙基、丁基或异丙基等，所述烷烃氧基例如可以是甲氧基、乙氧基、丙氧基、丁氧基或异丙氧基等，所述烯烃基可以是乙烯基、丙烯基或丁烯基等，所述烯烃氧基例如可以是2-(烯丙氧基)，所述芳基例如可以是苯基、对甲苯基或联苯基等。更具体的，具有式(1)所示结构的单体选自于苯基三氯硅烷(CAS：98-13-5)、氯二苯基硅烷(CAS：1631-83-0)、二苯二氯硅烷(CAS：80-10-4)、三苯基乙烯基硅烷(CAS：18666-68-7)、二苯基二乙烯基硅烷(CAS：17937-68-7)、二苯基二甲氧基硅烷(CAS：6843-66-9)或三甲氧基苯基硅烷(CAS：2996-92-1)中的一种或几种。
本发明具体实施方式的等离子体聚合涂层，在一些具体实施方式中，所述R 1、R 2、R 3和R 4分别独立的选自于氢原子、卤素原子、C 1-C 4的烷烃基、C 1-C 4的烷烃氧基、C 1-C 4的烯烃基、C 1-C 4的烯烃氧基、C 2-C 10的环氧烃氧烃基或C 2-C 10的环氧烃基；其中R 1、R 2、R 3和R 4中的至少一个为C 2-C 10的环氧烃氧烃基或C 2-C 10的环氧烃基。作为举例，所述烷烃基例如可以是甲基、乙基、丙基、丁基或异丙基等，所述烷烃氧基例如可以是甲氧基、乙氧基、丙氧基、丁氧基或异丙氧基等，所述烯烃基可以是乙烯基、丙烯基或丁烯基等，所述烯烃氧基例如可以是2-(烯丙氧基)，所述环氧烃氧烃基例如可以是(2,3-环氧丙氧)乙基、(2,3-环氧丙氧)丙基、(3,4-环氧丁氧)乙基或(3,4-环氧丁氧)丙基等，所述环氧烃基例如可以是2,3-环氧丙基、3,4-环氧乙基、3,4-环氧丁基或3，4-环氧环己基等。更具体的，具有式(1)所示结构的单体选自于3-(2,3-环氧丙氧)丙基甲基二甲氧基硅烷(CAS：65799-47-5)、3-(2,3-环氧丙氧)丙基三甲氧基硅烷(CAS：2530-83-8)、β-(3、4环氧环己基)-乙基三甲氧基硅烷(CAS：3388-04-3)或2-(3,4-环氧环己烷基)乙基三乙氧基硅烷(CAS：10217-34-2)中的一种或几种。在一些具体实施方式中，所述环氧为脂环族环 氧，如3，4-环氧环己基，这样具有更好的耐磨性能提升作用。
本发明具体实施方式的等离子体聚合涂层，在一些具体实施方式中，所述反应性单体还包括氟代烃、氟代丙烯酸酯或氟代硅烷中的一种或几种含氟单体，在一些具体实施方式中，所述氟代丙烯酸酯的结构如式(2)所示，
Figure PCTCN2022092128-appb-000004
其中，Z为连接部分，R 5、R 6和R 7分别独立的选自于氢原子、卤素原子、C 1-C 10的烃基或C 1-C 10的卤原子取代烃基，x为1-20的整数。
本发明具体实施方式的等离子体聚合涂层，所述Z为连接部分，用于连接酯键和全氟碳烷基，在一些具体实施方式中，所述Z为连接键、C 1-C 4的亚烷基或具有取代基的C 1-C 4的亚烷基。所述亚烷基包括直链的亚烷基，例如亚甲基、亚乙基、亚丙基或亚丁基等，或含有支链的亚烷基，例如亚异丙基或亚异丁基等，所述取代基例如包括卤素原子、羟基、羧基或酯基等等。
本发明具体实施方式的等离子体聚合涂层，所述反应性单体同时包括结构如式(2)所示的氟代丙烯酸酯单体以及具有式(1)所示结构的单体时，特别是所述x为4以上，进一步为6以上，所述x具体例如6、7、8、9、10、11、12、13、14、15、16、17、18、19或20时，所述等离子聚合涂层经过反复摩擦后，依然能保持优异的防水防油性能。
本发明具体实施方式的等离子体聚合涂层，作为具体的非限制性举例，所述氟代丙烯酸酯选自于3-(全氟-5-甲基己基)-2-羟基丙基甲基丙烯酸酯(CAS：16083-81-1)、2-(全氟癸基)乙基甲基丙烯酸酯(CAS：2144-54-9)、2-(全氟己基)乙基甲基丙烯酸酯(CAS：2144-53-8)、2-(全氟十二烷基)乙基丙烯酸酯(CAS：34395-24-9)、2-全氟辛基丙烯酸乙酯(CAS：27905-45-9)、1H,1H,2H,2H-全氟辛醇丙烯酸酯(CAS：17527-29-6)、2-(全氟丁基)乙基丙烯酸酯(CAS：52591-27-2)或(全氟环己基)甲基丙烯酸酯(CAS：40677-94-9)中的一种或几种。
本发明具体实施方式的等离子体聚合涂层，在一些具体实施方式中，所述基材为金属，具体例如，铁、镁、铝、铜或其合金，在另外的一些具体实施方式中，所述基材为各种塑料、织物、玻璃、电气组件或光学仪器等。具体地，电气组件可以是印刷电路板(PCB)、电子产品或电子组装半成品等。当所述基材是电子产品时，举例但是并不限制于手机、平板电脑、键盘、电子阅读器、可穿戴设备、显示器等。所述基材也可以是电气组件的任一合适的电气部件，具体地，所述电气部件可以是电阻器、电容器、晶体管、二极管、放大器、继电器、变压器、电池、熔断器、集成电路、开关、LED、LED显示器、压电元件、光电子部件或天线或振荡器等。
本发明具体实施方式的等离子体聚合涂层，在一些具体实施方式中，所述基材为玻璃屏，特别是手机屏，目前智能手机已经得到了普及，针对手机防水防指纹的问题，很多手机厂商会选择镀有防指纹膜的玻璃作为手机屏幕。目前主流的防指纹工艺有两种：一种是物理气相沉积工艺，另一种是湿法喷涂工艺，这两种工艺相对来说价格比较昂贵且实验条件比较苛刻，而对于一些廉价低端手机而言，屏幕上是没有防指纹工艺处理的，大大降低了手机使用过程中的防水防油性。本发明具体实施方式的等离子体聚合涂层，涂层制备更为容易，涂层均匀、厚度薄、应力小，对基材表面几乎没有损伤和基材性能几乎没有影响，同时具有优异的耐磨性能，特别适用作为手机等玻璃屏的防护涂层。
本发明具体实施方式的等离子体聚合涂层，在一些具体实施方式中，所述涂层由基材接触所述式(1)所示结构的单体和所述氟代丙烯酸酯的单体的等离子体沉积形成，在一些具体实施方式中，所述式(1)所示结构的单体与所述氟代丙烯酸酯的单体的摩尔比在3：10～10：3之间，具体例如可以是3：10、4：10、5：10、6：10、7：10、8：10、9：10、10：10、10：9、10：8、10：7、10：6、10：5、10：4或10：3等等。在另外一些具体实施方式中，也可以根据实际需要，所述涂层由基材接触所述式(1)所示结构的单体和其它单体的等离子体形成。
本发明的具体实施方式还提供一种任一以上所述等离子体聚合涂层的制备方法，包括：
提供基材，将基材置于等离子体反应器中；将所述单体汽化进入等离子体反应器，等离子体放电，在所述基材的表面等离子体聚合形成涂层。
本发明具体实施方式的所述等离子体聚合涂层的制备方法，所述方法提供了一种增加等离子体聚合涂层耐磨性的方法。
本发明具体实施方式的所述等离子体聚合涂层的制备方法，对于所述单体及基材如前所述。
本发明具体实施方式的所述等离子体聚合涂层的制备方法，对于某些基材，例如手机屏或线路板，为进一步增强等离子体涂层与基材的结合力，在一些具体实施方式中，在涂层前对所述基材为采用连续等离子体进行预处理，具体预处理方式例如，在惰性气体气氛下，采用等离子体放电功率为20～500W，放电方式为连续式，持续放电时间1～60min，或者采用热、氧或高能辐射等方式等等。
本发明具体实施方式的所述等离子体聚合涂层的制备方法，在一些具体实施方式中，所述等离子体为以连续波激发的等离子体，在另外一些具体实施方式中，所述等离子体是以脉冲方式激发的等离子体，单体流量为50～500μL/min，具体例如可以是100μL/min、200μL/min、300μL/min或400μL/min等等；腔体内的温度控制在20℃-80℃，具体例如可以是20℃、30℃、40℃、50℃、60℃、70℃或80℃等等；单体汽化温度为50℃-180℃，具体例如可以是50℃、60℃、70℃、80℃、90℃、100℃、110℃、120℃、130℃、140℃、150℃、160℃、170℃、180℃等等，且是在真空条件下发生汽化，所述脉冲等离子体通过施加脉冲电压放电产生，其中，脉冲功率为10W～300W，具体例如可以是10W、20W、30W、50W、70W、80W、100W、120W、140W、160W、180W、190W、200W、210W、220W、230W、240W、250W、260W、270W、280W、290W或300W等等；脉冲占空比为0.1％～85％，具体例如可以是0.1％、0.5％、1％、5％、10％、15％、20％、25％、30％、35％、40％、45％、50％、55％、60％、65％、70％、75％、80％或85％等等；等离子放电时间为100s-36000s，具体例如可以是100s、500s、1000s、1800s、2000s、1000s、2000s、3000s、4000s、5000s、6000s、7000s、7200s、10800s、14400s、18000s、21600s、25200s、28800s、32400s或36000s等等。
本发明具体实施方式的所述等离子体聚合涂层的制备方法，在一些具体实施方式中，所述等离子放电方式可以现有的各种放电方式，具体例如，无电极放电(如射频电感耦合放电、微波放电)、单电极放电(如电晕放电、单极放电所形成的等离子体射流)、双电极放电(如介质阻挡放电、裸露电极射频辉光放电)以及多电极放电(如采用浮动电极作为第三个电极的放电)。
本发明的具体实施方式还提供一种器件，所述器件的至少部分表面具有任一以上所述的等离子体聚合涂层，在一些具体实施方式中，所述器件的部分表面或全部表面沉积有上述的等离子体聚合涂层。
以下通过具体实施例对本发明做进一步说明。
实施例
实施例1
方案一：
将手机屏放置于等离子体腔室内，对腔体进行连续抽真空至5毫托，通入氦气，流量为40sccm，开启等离子体放电，脉冲功率180W，占空比1.5％；将单体β-(3、4环氧环己基)-乙基三甲氧基硅烷和单体2-全氟辛基丙烯酸乙酯，在汽化温度为180℃下进行汽化后导入腔体内进行等离子体化学气相沉积，其中单体β-(3、4环氧环己基)-乙基三甲氧基硅烷流量为75μL/min，单体2-全氟辛基丙烯酸乙酯流量为75μL/min；反应时间5400s；放电结束后通入压缩空气，使腔体恢复常压，打开腔体，取出手机屏。
方案二：
将另一块手机屏放置于等离子体腔室内，对腔体进行连续抽真空至5毫托，通入氦气，流量为40sccm，开启等离子体放电，脉冲功率180W，占空比1.5％；将单体2-全氟辛基丙烯酸乙酯，在汽化温度为180℃下进行汽化后导入腔体内进行等离子体化学气相沉积，其中单体2-全氟辛基丙烯酸乙酯流量为150μL/min；反应时间5400s；放电结束后通入压缩空气，使腔体恢复常压，打开腔体，取出手机屏。
方案三
将手机屏放置于等离子体腔室内，对腔体进行连续抽真空至5毫托，通 入氦气，流量为40sccm，开启等离子体放电，脉冲功率180W，占空比1.5％；将单体3-(2,3-环氧丙氧)丙基三甲氧基硅烷和单体2-全氟辛基丙烯酸乙酯，在汽化温度为180℃下进行汽化后导入腔体内进行等离子体化学气相沉积，其中单体3-(2,3-环氧丙氧)丙基三甲氧基硅烷流量为75μL/min，单体2-全氟辛基丙烯酸乙酯流量为75μL/min；反应时间5400s；放电结束后通入压缩空气，使腔体恢复常压，打开腔体，取出手机屏。
方案四
将手机屏放置于等离子体腔室内，对腔体进行连续抽真空至5毫托，通入氦气，流量为40sccm，开启等离子体放电，脉冲功率180W，占空比1.5％；将单体四甲氧基硅烷和单体2-全氟辛基丙烯酸乙酯，在汽化温度为180℃下进行汽化后导入腔体内进行等离子体化学气相沉积，其中单体四甲氧基硅烷流量为75μL/min，单体2-全氟辛基丙烯酸乙酯流量为75μL/min；反应时间5400s；放电结束后通入压缩空气，使腔体恢复常压，打开腔体，取出手机屏。
对方案一、方案二、方案三和方案四的手机屏进行耐磨性测试，在耐磨试验机上进行，摩擦材料为无尘布，载荷100g，转速50r/min。每摩擦100次记录一次水滴角和正十六烷油滴角。
测试结果如下：
Figure PCTCN2022092128-appb-000005
由上表结果可知，方案一中，包含带有脂肪环环氧基的有机硅单体β-(3、4环氧环己基)-乙基三甲氧基硅烷的等离子体聚合涂层具有最好的耐磨性能，摩擦1000次后水滴角保持为108°，正十六烷油滴角保持为72°。方案三中，包含带有链烃基环氧基的有机硅单体3-(2,3-环氧丙氧)丙基三甲氧基硅烷的等离子体聚合涂层具有良好的耐磨性能，摩擦1000次后水滴角保持为102°，正 十六烷油滴角保持为65°，但效果略差于方案一。方案二和方案四中，不含有机硅单体或包含非环氧有机硅单体四甲氧基硅烷，其等离子体聚合涂层的耐磨性能较差，摩擦1000次后水滴角分别保持仅为60°和67°，正十六烷油滴角保持仅为52°和56°。
实施例2
方案一：
将手机屏放置于等离子体腔室内，对腔体进行连续抽真空至5毫托，通入氦气，流量为40sccm，开启等离子体放电，脉冲功率180W，占空比1％；将单体苯基三甲氧基硅烷和单体1H,1H,2H,2H-全氟辛醇丙烯酸酯，在汽化温度为145℃下进行汽化后导入腔体内进行等离子体化学气相沉积，其中单体苯基三甲氧基硅烷流量为80μL/min，单体1H,1H,2H,2H-全氟辛醇丙烯酸酯流量为80μL/min；反应时间6000s；放电结束后通入压缩空气，使腔体恢复常压，打开腔体，取出手机屏。
方案二：
将另一块手机屏放置于等离子体腔室内，对腔体进行连续抽真空至5毫托，通入氦气，流量为40sccm，开启等离子体放电，脉冲功率180W，占空比1％；将单体1H,1H,2H,2H-全氟辛醇丙烯酸酯，在汽化温度为145℃下进行汽化后导入腔体内进行等离子体化学气相沉积，其中单体1H,1H,2H,2H-全氟辛醇丙烯酸酯流量为160μL/min；反应时间6000s；放电结束后通入压缩空气，使腔体恢复常压，打开腔体，取出手机屏。
方案三
将手机屏放置于等离子体腔室内，对腔体进行连续抽真空至5毫托，通入氦气，流量为40sccm，开启等离子体放电，脉冲功率180W，占空比1％；将单体四甲氧基硅烷和单体1H,1H,2H,2H-全氟辛醇丙烯酸酯，在汽化温度为145℃下进行汽化后导入腔体内进行等离子体化学气相沉积，其中单体四甲氧基硅烷流量为80μL/min，单体1H,1H,2H,2H-全氟辛醇丙烯酸酯流量为80μL/min；反应时间6000s；放电结束后通入压缩空气，使腔体恢复常压，打开腔体，取出手机屏。
对方案一、方案二和方案三的手机屏进行耐磨性测试，在耐磨试验机上进行，摩擦材料为无尘布，载荷500g，转速50r/min。每摩擦50次记录一次水滴角和正十六烷油滴角。
测试结果如下：
Figure PCTCN2022092128-appb-000006
由上表结果可知，方案一中，包含芳基的有机硅单体苯基三甲氧基硅烷的等离子体聚合涂层具有良好的耐磨性能，摩擦500次后水滴角保持为100°，正十六烷油滴角保持为68°。方案二和方案三中，不含有机硅单体或包含不带芳基的有机硅单体四甲氧基硅烷，其等离子体聚合涂层的耐磨性能较差，其中，不含有机硅单体的等离子体聚合涂层摩擦500次直接已经被磨损，包含不带芳基的有机硅单体四甲氧基硅烷的等离子体聚合涂层摩擦500次后水滴角保持仅55°，正十六烷油滴角保持仅为36°。
实施例3
方案一：
将手机屏放置于等离子体腔室内，对腔体进行连续抽真空至5毫托，通入氦气，流量为40sccm，开启等离子体放电，脉冲功率200W，占空比1.5％；将单体二苯基二甲氧基硅烷和单体2-全氟辛基丙烯酸乙酯，在汽化温度为180℃下进行汽化后导入腔体内进行等离子体化学气相沉积，其中单体二苯基二甲氧基硅烷流量为75μL/min，单体2-全氟辛基丙烯酸乙酯流量为75μL/min；反应时间1800s；放电结束后通入压缩空气，使腔体恢复常压，打开腔体，取出手机屏。
方案二：
将另一块手机屏放置于等离子体腔室内，对腔体进行连续抽真空至5毫托，通入氦气，流量为40sccm，开启等离子体放电，脉冲功率200W，占空 比1.5％；将单体2-全氟辛基丙烯酸乙酯，在汽化温度为180℃下进行汽化后导入腔体内进行等离子体化学气相沉积，其中单体2-全氟辛基丙烯酸乙酯流量为150μL/min；反应时间1800s；放电结束后通入压缩空气，使腔体恢复常压，打开腔体，取出手机屏。
对方案一和方案二的手机屏进行耐磨性测试，在耐磨试验机上进行，摩擦材料为无尘布，载荷100g，转速50r/min。每摩擦10次记录一次水滴角和正十六烷油滴角。
测试结果如下：
Figure PCTCN2022092128-appb-000007
由上表结果可知，方案一中，包含芳基的有机硅单体二苯基二甲氧基硅烷的等离子体聚合涂层具有良好的耐磨性能，摩擦100次后水滴角保持为102°，正十六烷油滴角保持为69°。方案二中，不含有机硅单体的等离子体聚合涂层摩擦100次直接已经被磨损。
实施例4
方案一：
将手机屏放置于等离子体腔室内，对腔体进行连续抽真空至5毫托，通入氦气，流量为40sccm，开启等离子体放电，脉冲功率180W，占空比1.5％；将单体β-(3、4环氧环己基)-乙基三甲氧基硅烷、苯基三甲氧基硅烷和单体1H,1H,2H,2H-全氟辛醇丙烯酸酯，在汽化温度为180℃下进行汽化后导入腔体内进行等离子体化学气相沉积，其中单体β-(3、4环氧环己基)-乙基三甲氧基硅烷流量为45μL/min，单体苯基三甲氧基硅烷流量为45μL/min，单体1H,1H,2H,2H-全氟辛醇丙烯酸酯流量为60μL/min；反应时间5000s；放电结束后通入压缩空气，使腔体恢复常压，打开腔体，取出手机屏。
方案二：
将另一块手机屏放置于等离子体腔室内，对腔体进行连续抽真空至5毫 托，通入氦气，流量为40sccm，开启等离子体放电，脉冲功率180W，占空比1.5％；将单体1H,1H,2H,2H-全氟辛醇丙烯酸酯，在汽化温度为180℃下进行汽化后导入腔体内进行等离子体化学气相沉积，其中单体1H,1H,2H,2H-全氟辛醇丙烯酸酯流量为150μL/min；反应时间5000s；放电结束后通入压缩空气，使腔体恢复常压，打开腔体，取出手机屏。
对方案一和方案二的手机屏进行耐磨性测试，在耐磨试验机上进行，摩擦材料为无尘布，载荷100g，转速50r/min。每摩擦100次记录一次水滴角和正十六烷油滴角。
测试结果如下：
Figure PCTCN2022092128-appb-000008
由上表结果可知，方案一中，包含带有脂肪环环氧基的有机硅单体β-(3、4环氧环己基)-乙基三甲氧基硅烷以及带有苯基的有机硅单体苯基三甲氧基硅烷的等离子体聚合涂层具有良好的耐磨性能，摩擦2000次后水滴角保持为105°，正十六烷油滴角保持为69°。方案二中，不含有机硅单体的等离子体聚合涂层摩擦2000次直接已经被磨损。
实施例5
方案一：
将Fe片(30*20*2mm)放置于等离子体腔室内，对腔体进行连续抽真空至5毫托，通入氦气，流量为40sccm，开启等离子体放电，脉冲功率180W，占空比3％；将单体β-(3、4环氧环己基)-乙基三甲氧基硅烷和单体2-全氟辛基丙烯酸乙酯，在汽化温度为180℃下进行汽化后导入腔体内进行等离子体化学气相沉积，其中单体β-(3、4环氧环己基)-乙基三甲氧基硅烷流量为100μL/min，单体2-全氟辛基丙烯酸乙酯流量为100μL/min；反应时间3600s；放电结束后通入压缩空气，使腔体恢复常压，打开腔体，取出Fe片。
方案二：
将另一块Fe片(30*20*2mm)放置于等离子体腔室内，对腔体进行连续抽真空至5毫托，通入氦气，流量为40sccm，开启等离子体放电，脉冲功率180W，占空比3％；将单体2-全氟辛基丙烯酸乙酯，在汽化温度为180℃下进行汽化后导入腔体内进行等离子体化学气相沉积，其中单体2-全氟辛基丙烯酸乙酯流量为200μL/min；反应时间3600s；放电结束后通入压缩空气，使腔体恢复常压，打开腔体，取出Fe片。
对方案一和方案二的Fe片进行耐磨性测试，在耐磨试验机上进行，摩擦材料为无尘布，载荷100g，转速50r/min。每摩擦100次记录一次水滴角和正十六烷油滴角。
测试结果如下：
Figure PCTCN2022092128-appb-000009
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 (19)

  1. 一种等离子体聚合涂层，其特征在于，所述涂层由基材接触反应性单体的等离子体反应沉积形成，
    其中，所述反应性单体包括具有式(1)所示结构的单体，
    Figure PCTCN2022092128-appb-100001
    式(1)中，R 1、R 2、R 3和R 4分别独立的选自于氢原子、卤素原子、C 1-C 20的取代或未取代的烃基、C 1-C 20的取代或未取代的烃氧基或C 4-C 20的芳香基；
    其中R 1、R 2、R 3和R 4中的至少一个包含环氧基或为C 4-C 20的芳香基。
  2. 根据权利要求1所述的等离子体聚合涂层，其特征在于，所述R 1、R 2、R 3和R 4分别独立的选自于氢原子、卤素原子、C 1-C 20的烃基、C 1-C 20的带有环氧结构取代基的烃基、C 1-C 20的烃氧基、C 1-C 20的带有环氧结构取代基的烃氧基或C 6-C 20的芳基。
  3. 根据权利要求2所述的等离子体聚合涂层，其特征在于，所述R 1、R 2、R 3和R 4分别独立的选自于氢原子、卤素原子、C 1-C 4的烷烃基、C 1-C 4的烷烃氧基、C 1-C 4的烯烃基、C 1-C 4的烯烃氧基或C 6-C 20的芳基；其中R 1、R 2、R 3和R 4中的至少一个为C 6-C 20的芳基。
  4. 根据权利要求3所述的等离子体聚合涂层，其特征在于，所述芳基为苯基。
  5. 根据权利要求4所述的等离子体聚合涂层，其特征在于，具有式(1)所示结构的单体选自于苯基三氯硅烷、氯二苯基硅烷、二苯二氯硅烷、三苯基乙烯基硅烷、二苯基二乙烯基硅烷、二苯基二甲氧基硅烷或三甲氧基苯基硅烷中的一种或几种。
  6. 根据权利要求2所述的等离子体聚合涂层，其特征在于，所述R 1、R 2、R 3和R 4分别独立的选自于氢原子、卤素原子、C 1-C 4的烷烃基、C 1-C 4的烷烃氧基、C 1-C 4的烯烃基、C 1-C 4的烯烃氧基、C 2-C 10的环氧烃氧烃基或C 2-C 10 的环氧烃基；其中R 1、R 2、R 3和R 4中的至少一个为C 2-C 10的环氧烃氧烃基或C 2-C 10的环氧烃基。
  7. 根据权利要求6所述的等离子体聚合涂层，其特征在于，所述环氧为脂环族环氧。
  8. 根据权利要求6所述的等离子体聚合涂层，其特征在于，具有式(1)所示结构的单体选自于3-(2,3-环氧丙氧)丙基甲基二甲氧基硅烷、3-(2,3-环氧丙氧)丙基三甲氧基硅烷、β-(3、4环氧环己基)-乙基三甲氧基硅烷或2-(3,4-环氧环己烷基)乙基三乙氧基硅烷中的一种或几种。
  9. 根据权利要求1所述的等离子体聚合涂层，其特征在于，所述反应性单体还包括氟代烃、氟代丙烯酸酯或氟代硅烷中的一种或几种。
  10. 根据权利要求9所述的等离子体聚合涂层，其特征在于，所述氟代丙烯酸酯的结构如式(2)所示，
    Figure PCTCN2022092128-appb-100002
    其中，Z为连接部分，R 5、R 6和R 7分别独立的选自于氢原子、卤素原子、C 1-C 10的烃基或C 1-C 10的卤原子取代烃基，x为1-20的整数。
  11. 根据权利要求10所述的等离子体聚合涂层，其特征在于，所述Z为连接键、C 1-C 4的亚烷基或具有取代基的C 1-C 4的亚烷基，x在4以上。
  12. 根据权利要求11所述的等离子体聚合涂层，其特征在于，所述R 5、R 6和R 7分别独立的选自于氢原子或甲基。
  13. 根据权利要求12所述的等离子体聚合涂层，其特征在于，所述氟代丙烯酸酯选自于3-(全氟-5-甲基己基)-2-羟基丙基甲基丙烯酸酯、2-(全氟癸基)乙基甲基丙烯酸酯、2-(全氟己基)乙基甲基丙烯酸酯、2-(全氟十二烷基)乙基丙烯酸酯、2-全氟辛基丙烯酸乙酯、1H,1H,2H,2H-全氟辛醇丙烯酸酯、2-(全氟丁基)乙基丙烯酸酯或(全氟环己基)甲基丙烯酸酯中的一种或几种。
  14. 根据权利要求1所述的等离子体聚合涂层，其特征在于，所述基材为金属、 塑料、织物、玻璃、电气组件、光学仪器或电气部件。
  15. 根据权利要求14所述的等离子体聚合涂层，其特征在于，所述基材为玻璃屏。
  16. 一种权利要求1-15任意一项所述的等离子体聚合涂层的制备方法，其特征在于，包括：
    提供基材，将基材置于等离子体反应器中；将所述反应性单体汽化进入等离子体反应器，等离子体放电，在所述基材的表面等离子体聚合形成涂层。
  17. 根据权利要求16所述的制备方法，其特征在于，所述等离子体为脉冲等离子体。
  18. 根据权利要求17所述的制备方法，其特征在于，所述脉冲等离子体通过施加脉冲电压放电产生，其中，脉冲功率为10W～300W，脉冲占空比为0.1％～85％，等离子放电时间为100s～36000s。
  19. 一种器件，其特征在于，所述器件的至少部分表面具有权利要求1-15任意一项所述的等离子体聚合涂层。
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