WO2023066103A1 - 一种复合涂层、制备方法及器件 - Google Patents

一种复合涂层、制备方法及器件 Download PDF

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WO2023066103A1
WO2023066103A1 PCT/CN2022/124797 CN2022124797W WO2023066103A1 WO 2023066103 A1 WO2023066103 A1 WO 2023066103A1 CN 2022124797 W CN2022124797 W CN 2022124797W WO 2023066103 A1 WO2023066103 A1 WO 2023066103A1
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monomer
group
composite coating
coating according
plasma
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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 EP22882713.5A priority Critical patent/EP4421137A4/en
Priority to US18/698,615 priority patent/US20250011621A1/en
Priority to MX2024004653A priority patent/MX2024004653A/es
Publication of WO2023066103A1 publication Critical patent/WO2023066103A1/zh
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    • 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
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • 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
    • C09D135/00—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 a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D135/02—Homopolymers or copolymers of esters
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • 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
    • B05D2202/00—Metallic substrate
    • 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
    • B05D3/14—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 electrical means
    • B05D3/141—Plasma treatment
    • B05D3/145—After-treatment
    • B05D3/147—Curing
    • 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
    • B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties

Definitions

  • the invention belongs to the field of plasma chemistry, and in particular relates to a plasma polymerized composite coating, a preparation method and a device.
  • Electronic and electrical equipment and metal devices are very sensitive to damage caused by liquids, especially water pollution.
  • electronic or electrical devices may cause contact between electronic components during normal use or accidental exposure to liquids.
  • Protective coatings can protect the surface of different substrates and reduce their vulnerability to liquids.
  • the preparation of polymer protective coatings on the surface of substrates by vapor deposition is the mainstream method. This method is economical, applicable, and easy to operate, especially plasma chemical vapor deposition, which uses plasma to activate reactive organic monomer gases such as fluorinated compounds.
  • the substrate surface is deposited, this method is suitable for various substrates, and the deposited polymer protective coating is uniform, the coating preparation temperature is low, the coating thickness is thin, the stress is small, and there is almost no damage to the substrate surface and the substrate There is almost no impact on performance, but the coating has problems such as poor wear resistance, unstable corrosion resistance, and performance degradation during transportation.
  • a composite coating comprising coating I deposited on a substrate
  • said coating I is a plasma-polymerized coating formed by a plasma comprising monomer ⁇ , monomer ⁇ and monomer ⁇ ;
  • the monomer ⁇ has a structure shown in formula (1-1),
  • Ar is a structure with an aromatic ring
  • T 1 is -OC(O)- or -C(O)-O-
  • X 1 is a connecting part
  • Y 1 is a connecting part
  • R 1 , R 2 and R 3 are respectively Independently selected from hydrogen atom, halogen atom, C 1 -C 10 alkyl or C 1 -C 10 halogen atom substituted alkyl;
  • the monomer ⁇ has a structure shown in formula (2-1),
  • R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are independently selected from hydrogen atom, A halogen atom, a C 1 -C 10 alkyl group or a C 1 -C 10 halogen atom replacing an alkyl group;
  • the monomer ⁇ has a structure shown in formula (3-1),
  • R 10 , R 11 , R 12 and R 13 are independently selected from hydrogen atoms, halogen atoms, C 1 -C 20 substituted or unsubstituted hydrocarbon groups, C 1 -C 20 substituted or unsubstituted hydrocarbon groups Oxygen or a C 4 -C 20 substituted or unsubstituted aryl group, wherein at least one of R 10 , R 11 , R 12 and R 13 contains an epoxy group or is a C 4 -C 20 aryl group.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are independently selected from a hydrogen atom or a methyl group.
  • the X1 is a structure shown in the following formula (1-2),
  • X 11 is a link, -O- or -C(O)-
  • X 12 is a link, a C 1 -C 10 alkylene group or a C 1 -C 10 halogen atom-substituted alkylene group;
  • the Y 1 is a link, a C 1 -C 10 alkylene group or a C 1 -C 10 halogen atom-substituted alkylene group.
  • the Ar is a benzene ring structure or a benzene ring structure with substituents.
  • the monomer ⁇ has the structure shown in formula (1-3),
  • T 2 is -OC(O)- or -C(O)-O-
  • X 2 is a connection part
  • Y 2 is a connection part
  • R 21 , R 22 and R 23 are each independently selected from a hydrogen atom, a halogen atom, a C 1 -C 10 alkyl group or a C 1 -C 10 halogen atom-substituted alkyl group.
  • the X 2 is a structure shown in the following formula (1-4),
  • X 21 is a link, -O- or -C(O)-
  • X 22 is a link, a C 1 -C 10 alkylene group or a C 1 -C 10 halogen atom-substituted alkylene group;
  • the Y 2 is a link, a C 1 -C 10 alkylene group or a C 1 -C 10 halogen atom-substituted alkylene group.
  • the R 21 , R 22 and R 23 are independently selected from a hydrogen atom or a methyl group.
  • the monomer ⁇ is selected from at least one of 2-phenoxyethyl acrylate, phenyl acrylate, diallyl terephthalate or phenyl methacrylate.
  • the S contains two of -O-C(O)- or -C(O)-O-, and x is more than 4.
  • the S has a structure shown in formula (2-2),
  • R 24 is a C 2 -C 10 alkylene group or a C 2 -C 10 halogen atom-substituted alkylene group, and y is an integer from 0 to 10.
  • the monomer ⁇ is selected from 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, dimethyl Diethylene glycol acrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, Methacrylic anhydride, diprop-2-enyl-2-methylene succinate, diprop-2-enyl 2-benzylidene malonate, or diethyl diallyl malonate at least one of the
  • the composite coating also includes coating II, and the coating II is contacted by the coating I to the plasma containing the monomer ⁇ and the monomer ⁇ , so that the plasma formed on the coating I is polymerized coating;
  • the monomer ⁇ has a structure shown in formula (4-1),
  • Z is a connecting part
  • R 14 , R 15 and R 16 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 monomer ⁇ has a structure shown in formula (5-1),
  • R 17 , R 18 , R 19 and R 20 are independently selected from hydrogen atom, halogen atom, C 1 -C 20 substituted or unsubstituted hydrocarbon group, C 1 -C 20 substituted or unsubstituted hydrocarbon Oxygen or a C 4 -C 20 substituted or unsubstituted aryl group, wherein at least one of R 17 , R 18 , R 19 and R 20 contains an epoxy group or is a C 4 -C 20 aryl group.
  • R 14 , R 15 and R 16 are independently selected from a hydrogen atom or a methyl group.
  • the Z is a link, a C 1 -C 4 alkylene group or a C 1 -C 4 alkylene group with substituents.
  • the monomer ⁇ 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-perfluorooctyl One or more of alcohol acrylate, 2-(perfluorobutyl) ethyl acrylate, (2H-perfluoropropyl)-2-acrylate or (perfluorocyclohexyl) methacrylate.
  • R 10 , R 11 , R 12 , R 13 , R 17 , R 18 , R 19 and R 20 are independently selected from hydrogen atoms, halogen atoms, C 1 -C 20 hydrocarbon groups, C 1 -C 20 hydrocarbon group with epoxy structure substituent, C 1 -C 20 hydrocarbon oxy group, C 1 -C 20 hydrocarbon group with epoxy structure substituent or C 6 -C 20 aromatic base.
  • the R 10 , R 11 , R 12 , R 13 , R 17 , R 18 , R 19 and R 20 are independently selected from a hydrogen atom, a halogen atom, a C 1 -C 4 alkane group, C 1 -C 4 alkoxyl, C 1 -C 4 alkenyl, C 1 -C 4 alkenyloxy or C 6 -C 20 aryl; wherein R 10 , R 11 , R 12 and R 13 At least one of R 17 , R 18 , R 19 and R 20 is a C 6 -C 20 aryl group, and at least one of R 17 , R 18 , R 19 and R 20 is a C 6 -C 20 aryl group.
  • the aryl is phenyl
  • the monomers ⁇ and ⁇ are independently selected from phenyltrichlorosilane, chlorodiphenylsilane, diphenyldichlorosilane, triphenylvinylsilane, diphenyldivinyl Silane, Phenyltrivinylsilane, Methylphenyldivinylsilane, Dimethylphenylvinylsilane, Methoxytriphenylsilane, Diphenyldimethoxysilane, or Phenyltrimethoxysilane one or more of them.
  • the R 10 , R 11 , R 12 , R 13 , R 17 , R 18 , R 19 and R 20 are independently selected from a hydrogen atom, a halogen atom, a C 1 -C 4 alkane group, C 1 -C 4 alkoxyl, C 1 -C 4 alkenyl, C 1 -C 4 alkenyloxy, C 2 -C 10 epoxyalkoxy or C 2 -C 10 epoxyalkyl ; wherein at least one of R 10 , R 11 , R 12 and R 13 is C 2 -C 10 epoxyalkylene oxyalkylene or C 2 -C 10 epoxyalkylene, R 17 , R 18 , R 19 and R At least one of 20 is a C 2 -C 10 epoxyalkoxyalkyl group or a C 2 -C 10 epoxyalkyl group.
  • the epoxy is cycloaliphatic epoxy.
  • the monomers ⁇ and ⁇ are independently selected from 3-(2,3-glycidoxy)propylmethyldimethoxysilane, 3-(2,3-epoxy Propoxy)propylmethyldiethoxysilane, 3-(2,3-Glycidoxy)propyltrimethoxysilane, 3-(2,3-Glycidoxy)propyltriethoxy
  • the substrate is metal, plastic, fabric, glass, electrical components, optical instruments or electrical components.
  • a method for preparing any of the above composite coatings comprising:
  • the substrate place the substrate in the plasma reaction chamber, evacuate to 20-250 mTorr, and pass in the inert gas He, Ar, O 2 or a mixture of several gases;
  • the vapors of monomer ⁇ , monomer ⁇ and monomer ⁇ are introduced into the reaction chamber, plasma discharge is turned on, and plasma polymerized coating I is formed.
  • the method further includes: introducing the vapors of the monomer ⁇ and the monomer ⁇ into the reaction chamber, turning on the plasma discharge, and forming the plasma-polymerized coating II on the coating I.
  • 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 frequency is 15Hz-60kHz, the pulse duty cycle is 1%-85%, and the plasma discharge time is 100s-36000s .
  • a device at least part of the surface of the device has any of the composite coatings described above.
  • the composite coating according to the specific embodiment of the present invention two monomers, an unsaturated ester compound with an aromatic ring and an organosilane with an aromatic group or an epoxy group, are simultaneously introduced to form a plasma coating, and the unsaturated ester compound has a There are aromatic rings. Due to the good stability of the aromatic rings, the coating can have better hardness, corrosion resistance, heat resistance and temperature resistance. At the same time, the hydrophobicity is improved and the water solubility is reduced. Moreover, the monomer contains ester groups or carboxyl groups. It can form hydrogen bonding force, and at the same time, the two ends of the organosilane material have good chemical bonding force to organic matter and inorganic matter respectively, so it has a good adhesion and bonding effect on the substrate.
  • the composite coating according to the specific embodiment of the present invention two monomers, fluoride and organosilane, are simultaneously introduced to form a plasma coating.
  • the organosilane forms a stable combination on the surface of the substrate or with the anti-corrosion layer.
  • fluorine groups It can improve the hydrophobic and oleophobic properties, and at the same time, there is a good chemical bond between fluoride and silane, which improves the wear resistance of the coating.
  • the composite coating according to the specific embodiment of the present invention is formed by the plasma of unsaturated ester monomers with aromatic rings, ester coupling agent monomers and organic silane monomers with aromatic groups or epoxy groups.
  • the inner layer is a coating formed by the plasma of fluorine-containing acrylate monomer and organosilane monomer with aromatic group or epoxy group as the outer layer, and the composite coating formed by it has excellent anti-corrosion performance and excellent wear resistance.
  • Fig. 1 is the Tafel graph obtained by electrochemical testing of coated Mg flakes and uncoated Mg flakes in Example 2.
  • the specific embodiment of the present invention provides a kind of composite coating, and described composite coating comprises coating I deposited on the substrate,
  • said coating I is a plasma-polymerized coating formed by a plasma comprising monomer ⁇ , monomer ⁇ and monomer ⁇ ;
  • the monomer ⁇ has a structure shown in formula (1-1),
  • Ar is a structure with an aromatic ring
  • T 1 is -OC(O)- or -C(O)-O-
  • X 1 is a connecting part
  • Y 1 is a connecting part
  • R 1 , R 2 and R 3 are respectively Independently selected from hydrogen atom, halogen atom, C 1 -C 10 alkyl or C 1 -C 10 halogen atom substituted alkyl;
  • the monomer ⁇ has a structure shown in formula (2-1),
  • R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are independently selected from hydrogen atom, A halogen atom, a C 1 -C 10 alkyl group or a C 1 -C 10 halogen atom replacing an alkyl group;
  • the monomer ⁇ has a structure shown in formula (3-1),
  • R 10 , R 11 , R 12 and R 13 are independently selected from hydrogen atoms, halogen atoms, C 1 -C 20 substituted or unsubstituted hydrocarbon groups, C 1 -C 20 substituted or unsubstituted hydrocarbon groups Oxygen or a C 4 -C 20 substituted or unsubstituted aryl group, wherein at least one of R 10 , R 11 , R 12 and R 13 contains an epoxy group or is a C 4 -C 20 aryl group.
  • the composite coating of the specific embodiment of the present invention also includes coating II, and the coating II contacts the plasma containing monomer ⁇ and monomer ⁇ from the coating I body, thereby forming a plasma-polymerized coating on coating I;
  • the monomer ⁇ has a structure shown in formula (4-1),
  • Z is a connecting part
  • R 14 , R 15 and R 16 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 monomer ⁇ has a structure shown in formula (5-1),
  • R 17 , R 18 , R 19 and R 20 are independently selected from hydrogen atom, halogen atom, C 1 -C 20 substituted or unsubstituted hydrocarbon group, C 1 -C 20 substituted or unsubstituted hydrocarbon Oxygen or a C 4 -C 20 substituted or unsubstituted aryl group, wherein at least one of R 17 , R 18 , R 19 and R 20 contains an epoxy group or is a C 4 -C 20 aryl group.
  • described Ar is the benzene ring or heteroaromatic ring that has substituent on aromatic ring, in other specific embodiments, described Ar is aromatic ring A benzene or heteroaryl ring with no substituents on it.
  • the X1 and Y1 are connecting parts, X1 is used to connect the structure Ar with an aromatic ring and the ester bond T1 , and Y1 is used to connect the ester bond T1 and the saturated Carbon-carbon double bond, in some specific embodiments, described X is the structure shown in following formula (1-2),
  • X 11 is a link, -O- or -C(O)-
  • X 12 is a link, a C 1 -C 10 alkylene group or a C 1 -C 10 halogen atom-substituted alkylene group
  • the Y 1 is a linking bond, a C 1 -C 10 alkylene group or a C 1 -C 10 halogen atom-substituted alkylene group.
  • 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 R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 14 , R 15 and R 16 are independently selected from a hydrogen atom or a methyl group.
  • the monomer ⁇ has a structure shown in formula (1-3),
  • T 2 is -OC(O)- or -C(O)-O-
  • X 2 is the connecting part, used to connect the benzene ring and the ester bond T 2
  • Y 2 is the connecting part, used to connect the ester bond T 2 and carbon-carbon double bonds
  • R 21 , R 22 and R 23 are each independently selected from a hydrogen atom, a halogen atom, a C 1 -C 10 alkyl group or a C 1 -C 10 halogen atom-substituted alkyl group.
  • the alkyl group includes straight-chain alkyl groups, such as methyl, ethyl, propyl or butyl, etc., or branched-chain alkyl groups, such as isopropyl or isobutyl groups.
  • the two substituents on the benzene ring are para-substituted, and in some other embodiments, is an ortho-substitution or a meta-substitution.
  • Composite coating of specific embodiments of the present invention in some specific embodiments, described X 2 is the structure shown in following formula (1-4),
  • X 21 is a link, -O- or -C(O)-
  • X 22 is a link, a C 1 -C 10 alkylene group or a C 1 -C 10 halogen atom-substituted alkylene group
  • the Y 2 is a linking bond, a C 1 -C 10 alkylene group or a C 1 -C 10 halogen atom-substituted alkylene group.
  • 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. .
  • R 21 , R 22 and R 23 are each independently selected from a hydrogen atom or a methyl group.
  • the monomer ⁇ is selected from -2-phenoxyethyl acrylate (CAS No.: 48145-04-6), phenyl acrylate ( At least one of Diallyl Terephthalate (CAS No.: 937-41-7), Diallyl Terephthalate (CAS No.: 1026-92-2) or Phenyl Methacrylate (CAS No.: 2177-70-0).
  • the S contains two total of -O-C(O)- or -C(O)-O-, that is, S contains two -O-C( O)-, two -C(O)-O- or -O-C(O)- or -C(O)-O- each one; said x is more than 4, such as 4, 5, 6, 7 , 8, 9, 10, 11 or 12 and so on.
  • the composite coating of the specific embodiment of the present invention, in some specific embodiments, described S has the structure shown in formula (2-2),
  • R 24 is a C 2 -C 10 alkylene group or a C 2 -C 10 halogen atom-substituted alkylene group
  • the alkylene group includes straight-chain alkylene groups, such as methylene, ethylene, A propylene group or a butylene group, etc., or an alkylene group containing a branch, such as an isopropylene group or an isobutylene group, etc.
  • y is an integer from 0 to 10. Specifically, it is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
  • the monomer ⁇ is selected from 1,4-butanediol dimethacrylate (CAS No.: 2082-81-7), di 1,6-Hexanediol Methacrylate (CAS No.: 6606-59-3), Ethylene Glycol Dimethacrylate (CAS No.
  • Diethylene Glycol Dimethacrylate (CAS No.: 2358-84-1), Triethylene Glycol Dimethacrylate (CAS No.: 109-16-0), Tetraethylene Glycol Dimethacrylate (CAS No.: 109-17-1) , 1,3-butylene glycol dimethacrylate (CAS No.: 1189-08-8), neopentyl glycol dimethacrylate (CAS No.: 1985-51-9), methacrylic anhydride (CAS No.: 760-93-0), Diprop-2-enyl-2-methylene succinate, Diprop-2-enyl 2-benzylidene malonate (CAS No.: 52505-39 -2) or at least one of diethyl diallylmalonate (CAS No.: 3195-24-2).
  • said Z is a linking moiety for connecting ester bonded perfluorocarbon alkyl groups, and in some specific embodiments, said Z is a linking bond, C 1 -C 4 alkylene group or a substituent C 1 -C 4 alkylene group.
  • 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 x is more than 4, further more than 6, and the specific x is for example 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 are beneficial to improve the hydrophobicity of the coating.
  • the monomer ⁇ is selected from 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl methacrylate (CAS No.: 16083-81-1), 2-(perfluorodecyl) ethyl methacrylate (CAS No.: 2144-54-9), 2-(perfluorohexyl) ethyl methacrylate (CAS No.
  • R 10 , R 11 , R 12 and R 13 are independently selected from hydrogen atoms, halogen atoms, C 1 -C 20 substituted or unsubstituted hydrocarbon groups, C 1 -C 20 substituted or unsubstituted alkoxy group or C 4 -C 20 substituted or unsubstituted aryl group, wherein, at least one of R 10 , R 11 , R 12 and R 13 contains an epoxy group or is C 4 -C 20 aryl group;
  • R 17 , R 18 , R 19 and R 20 are independently selected from hydrogen atom, halogen atom, C 1 -C 20 substituted or unsubstituted hydrocarbon group, C 1 -C 20 substitution or an unsubstituted alkoxy group or a C 4 -C 20 substituted or unsubstituted aromatic group, wherein at least one of R 17 , R 18 , R 19 and R 20 contains an epoxy group or is C 4 -C
  • said R 10 , R 11 , R 12 , R 13 , R 17 , R 18 , R 19 and R 20 are independently selected from hydrogen atoms , halogen atom, C 1 -C 20 hydrocarbon group, C 1 -C 20 hydrocarbon group with epoxy structure substituent, C 1 -C 20 alkoxy group, C 1 -C 20 with epoxy structure substituent Hydrocarbyloxy group or C 6 -C 20 aryl group.
  • said R 10 , R 11 , R 12 , R 13 , R 17 , R 18 , R 19 and R 20 are independently selected from hydrogen atoms , halogen atom, C 1 -C 4 alkane group, C 1 -C 4 alkane oxy group, C 1 -C 4 alkene group, C 1 -C 4 alkene oxy group or C 6 -C 20 aryl group ; wherein at least one of R 10 , R 11 , R 12 and R 13 is a C 6 -C 20 aryl group, and at least one of R 17 , R 18 , R 19 and R 20 is a C 6 -C 20 aryl group base.
  • 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 aryl group can be, for example, phenyl , p-tolyl or biphenyl, etc.
  • the monomers ⁇ and ⁇ are independently selected from phenyltrichlorosilane (CAS: 98-13-5), chlorodiphenylsilane (CAS: 1631- 83-0), diphenyldichlorosilane (CAS: 80-10-4), triphenylvinylsilane (CAS: 18666-68-7), diphenyldivinylsilane (CAS: 17937-68- 7), phenyltrivinylsilane (CAS: 18042-57-4), methylphenyldivinylsilane, dimethylphenylvinylsilane (CAS: 1125-26-4), methoxytrivinylsilane One of phenylsilane (CAS: 1829-41-0), diphenyldimethoxysilane (CAS: 6843-66-9) or trimethoxyphenylsilane (CAS: 2996-92-1) or several.
  • phenyltrichlorosilane CAS: 98-13-5
  • said R 10 , R 11 , R 12 , R 13 , R 17 , R 18 , R 19 and R 20 are independently selected from hydrogen atoms , halogen atom, C 1 -C 4 alkane group, C 1 -C 4 alkane oxy group, C 1 -C 4 alkene group, C 1 -C 4 alkene oxy group, C 2 -C 10 epoxy Oxyalkylene group or C 2 -C 10 epoxyalkylene group; wherein at least one of R 10 , R 11 , R 12 and R 13 is C 2 -C 10 epoxyalkoxyalkylene group or C 2 -C 10 ring Oxyalkyl, at least one of R 17 , R 18 , R 19 and R 20 is a C 2 -C 10 epoxy alkoxyl or a C 2 -C 10 epoxy alkyl.
  • 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 epoxy is cycloaliphatic epoxy, such as 3,4-epoxycyclohexyl.
  • the monomers ⁇ and ⁇ are independently selected from 3-(2,3-glycidoxy)propylmethyldimethoxysilane (CAS: 65799 -47-5), 3-(2,3-Glycidoxy)propylmethyldiethoxysilane (CAS: 2897-60-1), 3-(2,3-Glycidoxy)propane Trimethoxysilane (CAS: 2530-83-8), 3-(2,3-epoxypropoxy)propyltriethoxysilane (CAS: 2602-34-8), ⁇ -(3,4 Epoxycyclohexyl)-ethyltrimethoxysilane (CAS: 3388-04-3) or 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane (CAS: 10217-34- 2) One or more of them.
  • the substrate is metal, plastic, fabric, glass, electrical components, optical instruments or electrical components.
  • the metal can be, for example, iron, magnesium, aluminum, copper or alloys thereof
  • the electrical component can be, for example, a printed circuit board (PCB), an electronic product or an electronic assembly semi-finished product, etc.
  • the electronic product is such as a computer, Smartphones, tablet computers, keyboards, e-readers, wearable devices, displays, earphones, etc.
  • the electrical components can be, data lines (such as Type-C data lines, USB data lines, etc.), sound-transmitting nets, resistors , capacitors, transistors, diodes, amplifiers, relays, transformers, batteries, fuses, integrated circuits, switches, LEDs, LED displays, piezoelectric elements, optoelectronic components or antennas or oscillators, etc.
  • the substrate is a glass screen, especially a mobile phone screen.
  • a glass screen especially a mobile phone screen.
  • smart phones have been popularized. Aiming at the problem of waterproof and anti-fingerprint of mobile phones, many mobile phone manufacturers will The glass coated with anti-fingerprint film is selected as the mobile phone screen.
  • the traditional anti-fingerprint coating process mainly adopts physical vapor deposition process and wet spraying process, but these two processes are relatively expensive and the experimental conditions are relatively harsh; the present invention specifically
  • the plasma polymerized coating of the embodiment adopts the plasma chemical vapor deposition method, the coating preparation is easier, the coating is uniform, the thickness is thin, the stress is small, there is almost no damage to the substrate surface and almost no influence on the performance of the substrate, which greatly improves the performance of the coating. It improves the waterproof and oil-proof performance of the mobile phone during use, and has excellent wear resistance and anti-corrosion performance, and is especially suitable as a protective coating for glass screens such as mobile phones.
  • the ratio of monomer ⁇ , monomer ⁇ and monomer ⁇ can be adjusted.
  • the monomer ⁇ and monomer The molar ratio of ⁇ is between 3:10 and 10:3, for example, it 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, etc.
  • the molar ratio of monomer ⁇ to monomer ⁇ and monomer ⁇ is 1: Between 10 and 10:1, for example, 1:10, 2:10, 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, 10:3, 10:2, 10:1, etc.
  • the ratio of monomer ⁇ and monomer ⁇ can be adjusted.
  • the molar ratio of monomer ⁇ and monomer ⁇ Between 3:10 and 10:3, for example, 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 I is a plasma polymerized coating formed by the plasma of monomer ⁇ , monomer ⁇ and monomer ⁇ , and the coating II A plasma polymerized coating formed on coating I by exposing said coating I to the plasma of monomer ⁇ and monomer ⁇ .
  • the coating I is formed by the plasma of monomer ⁇ , monomer ⁇ , monomer ⁇ and other monomers
  • the coating II is formed by the plasma of the coating I is exposed to the plasma of monomer ⁇ , monomer ⁇ , and other monomers, thereby forming a plasma-polymerized coating on coating I.
  • the specific embodiment of the present invention also provides a kind of preparation method of above-mentioned composite coating, comprising:
  • the substrate place the substrate in the plasma reaction chamber, evacuate to 20-250 mTorr, and pass in the inert gas He, Ar, O 2 or a mixture of several gases;
  • the vapors of monomer ⁇ , monomer ⁇ and monomer ⁇ are introduced into the reaction chamber, plasma discharge is turned on, and plasma polymerized coating I is formed.
  • the method further includes: introducing the vapors of the monomer ⁇ and the monomer ⁇ into the reaction chamber, turning on the plasma discharge, and forming the plasma-polymerized coating II on the coating I.
  • the composite coating preparation method 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 the 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 1-60min, or using Heat, oxygen or high-energy radiation and so on.
  • the plasma is a pulsed plasma
  • the flow rate of the monomer is 50-3000ul/min, for example, it can be 100ul/min, 200ul/min min, 300ul/min, 400ul/min, 500ul/min, 1000ul/min, 1500ul/min, 2000ul/min, 2500ul/min or 3000ul/min, etc; It can be 20°C, 30°C, 40°C, 50°C, 60°C, 70°C or 80°C, etc.; 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C or 180°C, etc., and gasification occurs under vacuum conditions, the pulse plasma It is generated by applying a pulse voltage discharge, wherein the pulse power is 10W-300W, for example, it can be 10W, 20W, 30W, 40w, 50w, 60w, 70w, 80w,
  • the composite coating preparation method of the specific embodiment of the present invention in some specific embodiments, described plasma discharge mode can be existing various discharge modes, specifically for example, electrodeless discharge (as radio frequency inductive coupling 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 using a floating electrode as the third electrode discharge).
  • electrodeless discharge as radio frequency inductive coupling 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 using a floating electrode as the third electrode discharge.
  • 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 composite coating, in some specific embodiments, part or all of the surface of the device is only coated with the above protective coating.
  • Salt spray resistance test test according to GB/T 2423.18-2000 environmental test method for electrical and electronic products.
  • Coating thickness test use American Filmetrics F20-UV-film thickness measuring instrument for detection.
  • Circuit board friction test rub the circuit board on the wear-resistant testing machine, the friction material is dust-free cloth, the load is 200g, the number of frictions is 50 times, the speed is 40r/min, and the stroke is 30mm; the circuit board after friction is soaked in water, Provide it with a voltage of 5V, use a computer to detect the current, and record the failure time (current > 0.6mA).
  • Abrasion resistance test of mobile phone screen rub the mobile phone screen on a wear-resistant testing machine, the friction material is dust-free cloth, the load is 100g, the speed is 50r/min, and the water drop angle and n-hexadecane oil drop angle are recorded every 100 times of friction.
  • Electrochemical test Shanghai Chenhua CHI660E C20704 electrochemical analyzer, test the polarization curve in 3.6% NaCl neutral solution, the test conditions, the corrosion potential is negative 600mv ⁇ positive 600mv, the scan rate is 0.00033mv/s, and the scan time is 600s.
  • the discharge power in this pretreatment stage is 120W , continuous discharge for 800s;
  • the mixed monomer vapor of 1,6-hexanediol diacrylate and phenyl methacrylate (mass ratio 2:1), and phenyltrimethoxysilane vapor are introduced, and the monomer vaporization temperature is 180°C, the flow rate is 300ul/min respectively, the plasma discharge is turned on, the time is 3000s, the power supply is 40W, the frequency is 45Hz, the duty ratio is 35%, and the coating I is formed;
  • ⁇ -(3,4 epoxycyclohexyl)-ethyltrimethoxysilane vapor and 2-perfluorooctyl ethyl acrylate vapor are introduced into the plasma chamber, and the monomer gasification temperature is 180° C., ⁇ -( 3.
  • the flow rate of 4-epoxycyclohexyl)-ethyltrimethoxysilane is 75 ⁇ L/min
  • the flow rate of 2-perfluorooctylethyl acrylate vapor is 75 ⁇ L/min
  • the plasma discharge is turned on, the reaction time is 5400s, and the power supply is 180W. Frequency 45Hz, duty cycle 1.5%, forming coating II;
  • the compressed air is introduced to restore the chamber to normal pressure, open the chamber, take out the circuit board, Mg sheet, Fe sheet, and mobile phone screen sheet, test the coating thickness of the Mg sheet and Fe sheet, and conduct a salt spray test.
  • Table 1 the coating thickness of the test circuit board and the friction resistance test results are listed in Table 2, and the abrasion resistance test results of the mobile phone screen are listed in Table 3.
  • the mixed monomer vapor of 1,6-hexanediol diacrylate and phenyl acrylate (mass ratio 3:2), and diphenyldimethoxysilane vapor are introduced, and the monomer vaporization temperature is 180°C, the flow rate is 400ul/min respectively, the plasma discharge is turned on, the time is 3800s, the power supply is 37W, the frequency is 65Hz, the duty ratio is 45%, and the coating I is formed;
  • phenyltrimethoxysilane vapor and 1H, 1H, 2H, 2H-perfluorooctyl acrylate vapor were introduced into the plasma chamber, the monomer gasification temperature was 145°C, and the flow rate of phenyltrimethoxysilane vapor was 80 ⁇ L /min, 1H, 1H, 2H, 2H-perfluorooctyl alcohol acrylate vapor flow rate is 80 ⁇ L/min; turn on the plasma discharge, the reaction time is 6000s, the power supply is 180W, the frequency is 65Hz, the duty ratio is 1%, and the coating II is formed ;
  • the compressed air is introduced to restore the chamber to normal pressure, open the chamber, take out the circuit board, Mg sheet and Fe sheet, test the coating thickness of the Mg sheet and Fe sheet, and carry out the salt spray test.
  • the results are listed in Table 1
  • the test circuit board coating thickness and friction resistance test results are listed in Table 2
  • the Mg sheet after the coating and the uncoated Mg sheet are carried out electrochemical test, obtain Tafel curve as accompanying drawing 1, to this curve
  • the fitted electrochemical parameters are listed in Table 4.
  • the mixed monomer vapor of 1,6-hexanediol diacrylate and phenyl methacrylate (mass ratio 2:1), and 3-(2,3-epoxypropoxy)propyl Trimethoxysilane vapor the gasification temperature of the monomer is 180°C, the flow rate is 300ul/min respectively, the plasma discharge is turned on, the time is 3000s, the power supply is 40W, the frequency is 45Hz, and the duty ratio is 35%, to form the coating I;
  • 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane vapor and 2-perfluorooctyl ethyl acrylate vapor were introduced into the plasma chamber, and the vaporization temperature of the monomer was 180°C.
  • the vapor flow rate of 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane was 75 ⁇ L/min, and the vapor flow rate of 2-perfluorooctylethyl acrylate was 75 ⁇ L/min; the plasma discharge was turned on, and the reaction Time 5400s, power supply 180W, frequency 45Hz, duty cycle 1.5%, forming coating II;
  • the compressed air is introduced to restore the chamber to normal pressure, open the chamber, take out the circuit board, Mg sheet and Fe sheet, test the coating thickness of the Mg sheet and Fe sheet, and carry out the salt spray test.
  • the results are listed in Table 1
  • Test circuit board coating thickness and friction test results are listed in Table 2.
  • the mixed monomer vapor of 1,6-hexanediol diacrylate and phenyl acrylate (mass ratio 3:2), and ⁇ -aminopropyltriethoxysilane vapor are introduced to vaporize the monomer
  • the temperature is 180°C
  • the flow rates are both 400ul/min
  • the plasma discharge is turned on
  • the time is 3800s
  • the power supply is 37W
  • the frequency is 65Hz
  • the duty ratio is 45%, forming the coating I;
  • phenyltrimethoxysilane vapor and 1H, 1H, 2H, 2H-perfluorooctyl acrylate vapor were introduced into the plasma chamber, the monomer gasification temperature was 145°C, and the flow rate of phenyltrimethoxysilane vapor was 80 ⁇ L /min, 1H, 1H, 2H, 2H-perfluorooctyl alcohol acrylate vapor flow rate is 80 ⁇ L/min; turn on the plasma discharge, the reaction time is 6000s, the power supply is 180W, the frequency is 65Hz, the duty ratio is 1%, and the coating II is formed ;
  • the compressed air is introduced to restore the chamber to normal pressure, open the chamber, take out the circuit board, Mg sheet and Fe sheet, test the coating thickness of the Mg sheet and Fe sheet, and carry out the salt spray test.
  • the results are listed in Table 1
  • Test circuit board coating thickness and friction test results are listed in Table 2.
  • the mixed monomer vapor of 1,6-hexanediol diacrylate and phenyl methacrylate (mass ratio 2:1) was introduced.
  • the monomer vaporization temperature was 180°C, and the flow rate was 600ul/min.
  • the time is 3000s, the power supply is 40W, the frequency is 45Hz, the duty cycle is 35%, and the coating I is formed;
  • ⁇ -(3,4 epoxycyclohexyl)-ethyltrimethoxysilane vapor and 2-perfluorooctyl ethyl acrylate vapor are introduced into the plasma chamber, and the monomer gasification temperature is 180° C., ⁇ -( 3.
  • the flow rate of 4-epoxycyclohexyl)-ethyltrimethoxysilane is 75 ⁇ L/min
  • the flow rate of 2-perfluorooctylethyl acrylate vapor is 75 ⁇ L/min
  • the plasma discharge is turned on, the reaction time is 5400s, and the power supply is 180W. Frequency 45Hz, duty cycle 1.5%, forming coating II;
  • the compressed air is introduced to restore the chamber to normal pressure, open the chamber, take out the circuit board, Mg sheet and Fe sheet, test the coating thickness of the Mg sheet and Fe sheet, and carry out the salt spray test.
  • the results are listed in Table 1
  • Test circuit board coating thickness and friction test results are listed in Table 2.
  • the monomer gasification temperature is 180°C
  • the flow rate is 600ul/min
  • open Plasma discharge time 3000s
  • power supply 40W frequency 45Hz
  • duty cycle 35% forming coating I
  • ⁇ -(3,4 epoxycyclohexyl)-ethyltrimethoxysilane vapor and 2-perfluorooctyl ethyl acrylate vapor are introduced into the plasma chamber, and the monomer gasification temperature is 180° C., ⁇ -( 3.
  • the flow rate of 4-epoxycyclohexyl)-ethyltrimethoxysilane is 75 ⁇ L/min
  • the flow rate of 2-perfluorooctylethyl acrylate vapor is 75 ⁇ L/min
  • the plasma discharge is turned on, the reaction time is 5400s, and the power supply is 180W. Frequency 45Hz, duty cycle 1.5%, forming coating II;
  • the compressed air is introduced to restore the chamber to normal pressure, open the chamber, take out the circuit board, Mg sheet and Fe sheet, test the coating thickness of the Mg sheet and Fe sheet, and carry out the salt spray test.
  • the results are listed in Table 1
  • Test circuit board coating thickness and friction test results are listed in Table 2.
  • the monomer gasification temperature is 180°C
  • ⁇ -(3 , 4 epoxycyclohexyl)-ethyltrimethoxysilane flow rate is 75 ⁇ L/min
  • 2-perfluorooctyl ethyl acrylate vapor flow rate is 75 ⁇ L/min
  • plasma discharge is turned on, the reaction time is 16000s, the power supply is 180W, and the frequency 45Hz, duty cycle 1.5%, forming a coating
  • the compressed air is introduced to restore the chamber to normal pressure, open the chamber, take out the circuit board, Mg sheet, and Fe sheet, test the coating thickness of the Mg sheet, Fe sheet, and conduct the salt spray test.
  • the results are listed in Table 1.
  • Test circuit board coating thickness and friction test results are listed in Table 2.
  • the composite coating has the plasma of unsaturated ester monomers with aromatic rings, ester coupling agent monomers and general organosilane monomers.
  • the formed coating is used as the inner layer, and the coating formed by the plasma of the fluorine-containing acrylate monomer and the organosilane monomer with aromatic groups is used as the outer layer.
  • the inner layer of the composite coating does not contain organic Silane monomers, which use unsaturated ester monomers with aromatic rings and plasma-formed coatings of ester coupling agent monomers as the inner layer, and fluorine-containing acrylate monomers and organic resins with epoxy groups
  • the coating formed by the plasma of silane monomer is used as the outer layer.
  • the composite coating is made of unsaturated ester monomers without aromatic rings, ester coupling agent monomers and organosilane monomers with aromatic groups.
  • the coating formed by the plasma of the body is used as the inner layer, and the coating formed by the plasma of the fluorine-containing acrylate monomer and the organosilane monomer with epoxy groups is used as the outer layer.
  • the fluorine-containing acrylic acid The coating formed by the plasma of the ester monomer and the organosilane monomer with epoxy groups, the composite coating in the embodiment 1-3 uses the unsaturated ester monomer with aromatic ring, the ester coupling agent monomer and The coating formed by plasma of organosilane monomer with aromatic group or epoxy group is used as the inner layer, and the coating formed by plasma of fluorine-containing acrylate monomer and organosilane monomer with aromatic group or epoxy group As the outer layer, it has better salt spray resistance test results and friction resistance test results, indicating that the composite coatings of Examples 1-3 have the most excellent anti-corrosion performance and wear resistance.

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Abstract

本发明具体实施方式提供一种复合涂层、制备方法及器件，所述复合涂层以具有芳香环的不饱和酯类单体、酯类偶联剂单体以及具有芳香基或环氧基的有机硅烷单体的等离子体形成的涂层作为里层，以含氟丙烯酸酯类单体和具有芳香基或环氧基的有机硅烷单体的等离子体形成的涂层作为外层，所述复合涂层具有优异的防腐性能的同时具有优异的耐磨性能。

Description

一种复合涂层、制备方法及器件
本申请要求于2021年10月20日提交中国专利局、申请号为202111223170.2,发明名称为“一种复合涂层、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复合涂层、制备方法及器件。
背景技术
电子和电气设备以及金属器件等对于由液体尤其是水的污染所造成的损害是非常敏感的，比如，电子或电气器件在正常使用过程中或意外曝露接触液体时，可能导致电子元件之间的短路，以及对电路板、电子芯片等造成无法弥补的损害。保护涂层可以对不同基材表面进行保护，降低其对液体的易损性。利用气相沉积法在基材表面制备聚合物防护涂层是主流方法，该方法经济适用、易于操作等特点，尤其是等离子体化学气相沉积，利用等离子体活化反应有机单体气体例如氟代化合物在基材表面进行沉积，这种方法适用于各种基材，且沉积的聚合物防护涂层均匀，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，但是涂层存在耐磨性较差，耐腐蚀性能不稳定，运输过程性能下降等问题。
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具有优异的防腐性能及耐磨性的复合涂层、制备方法及器件，具体方案如下：
一种复合涂层，所述复合涂层包括沉积于基材上的涂层Ⅰ，
所述涂层Ⅰ由包含单体α、单体β和单体γ的等离子体形成的等离子体聚合涂层；
所述单体α具有式(1-1)所示的结构，
Figure PCTCN2022124797-appb-000001
其中，Ar为带芳环的结构，T 1为-O-C(O)-或-C(O)-O-，X 1为连接部分，Y 1为连接部分，R 1、R 2和R 3分别独立的选自为氢原子、卤素原子、C 1-C 10的烷基或C 1-C 10的卤原子取代烷基；
所述单体β具有式(2-1)所示的结构，
Figure PCTCN2022124797-appb-000002
其中，S中含有一个以上的-O-C(O)-或-C(O)-O-，R 4、R 5、R 6、R 7、R 8和R 9分别独立的选自为氢原子、卤素原子、C 1-C 10的烷基或C 1-C 10的卤原子取代烷基；
所述单体γ具有式(3-1)所示的结构，
Figure PCTCN2022124797-appb-000003
其中，R 10、R 11、R 12和R 13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的取代或未取代的芳香基，其中，R 10、R 11、R 12和R 13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、R 4、R 5、R 6、R 7、R 8和R 9分别独立的选自于氢原子或甲基。
可选的，所述X 1为下式(1-2)所示的结构，
*-X 11-X 12- *
      (1-2)
其中，X 11为连接键、-O-或-C(O)-，X 12为连接键、C 1-C 10的亚烷基或C 1-C 10的卤原子取代亚烷基；
所述Y 1为连接键、C 1-C 10的亚烷基或C 1-C 10的卤原子取代亚烷基。
可选的，所述Ar为苯环结构或带有取代基的苯环结构。
可选的，所述单体α具有式(1-3)所示的结构，
Figure PCTCN2022124797-appb-000004
其中，T 2为-O-C(O)-或-C(O)-O-，X 2为连接部分，Y 2为连接部分；
R 21、R 22和R 23分别独立的选自为氢原子、卤素原子、C 1-C 10的烷基或C 1-C 10的卤原子取代烷基。
可选的，所述X 2为下式(1-4)所示的结构，
*-X 22-X 21- *
      (1-4)
其中，X 21为连接键、-O-或-C(O)-，X 22为连接键、C 1-C 10的亚烷基或C 1-C 10的卤原子取代亚烷基；
所述Y 2为连接键、C 1-C 10的亚烷基或C 1-C 10的卤原子取代亚烷基。
可选的，所述R 21、R 22和R 23分别独立的选自为氢原子或甲基。
可选的，所述单体α选自于丙烯酸-2-苯氧基乙酯、丙烯酸苯酯、对苯二甲酸二烯丙酯或甲基丙烯酸苯酯中的至少一个。
可选的，所述S中含有-O-C(O)-或-C(O)-O-共两个，x在4以上。
可选的，所述S具有式(2-2)所示的结构，
Figure PCTCN2022124797-appb-000005
其中，R 24为C 2-C 10的亚烷基或C 2-C 10的卤原子取代亚烷基，y为0到10的整数。
可选的，所述单体β选自于二甲基丙烯酸1,4-丁二醇酯、二甲基丙烯酸1,6-己二醇酯、二甲基丙烯酸乙二醇酯、二甲基丙烯酸二乙二醇酯、二甲基丙烯酸三乙二醇酯、二甲基丙烯酸四乙二醇酯、二甲基丙烯酸1,3-丁二醇酯、二甲基丙烯酸新戊二醇酯、甲基丙烯酸酐、二丙-2-烯基-2-亚甲基丁二酸酯、2-亚苄基丙二酸二丙-2-烯基酯或二烯丙基丙二酸二乙酯中的至少一个。
可选的，所述复合涂层还包括涂层Ⅱ，所述涂层Ⅱ由所述涂层Ⅰ接触包含单体δ和单体ε的等离子体，从而在涂层Ⅰ上形成的等离子体聚合涂层；
所述单体δ具有式(4-1)所示的结构，
Figure PCTCN2022124797-appb-000006
其中，Z为连接部分，R 14、R 15和R 16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；
所述单体ε具有式(5-1)所示的结构，
Figure PCTCN2022124797-appb-000007
其中，R 17、R 18、R 19和R 20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的取代或未取代的芳香基，其中，R 17、R 18、R 19和R 20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 14、R 15和R 16分别独立的选自于氢原子或甲基。
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。
可选的，所述单体δ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、(2H-全氟丙基)-2-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R 10、R 11、R 12、R 13、R 17、R 18、R 19和R 20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 10、R 11、R 12、R 13、R 17、R 18、R 19和R 20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 10、R 11、R 12和R 13中的至少一个为C 6-C 20的芳基，R 17、R 18、R 19和R 20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，所述单体γ和单体ε分别独立的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、苯基三乙烯基硅烷、甲基苯基二乙烯基硅烷、二甲基苯基乙烯基硅烷、甲氧基三苯基硅烷、二苯基二甲氧基硅烷或苯基三甲氧基硅烷中的一种或几种。
可选的，所述R 10、R 11、R 12、R 13、R 17、R 18、R 19和R 20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 10、R 11、R 12和R 13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，R 17、R 18、R 19和R 20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，所述单体γ和单体ε分别独立的选自于3-(2,3-环氧丙氧)丙基甲基二甲氧基硅烷、3-(2,3-环氧丙氧)丙基甲基二乙氧基硅烷、3-(2,3-环氧丙氧)丙基三甲氧基硅烷、3-(2,3-环氧丙氧)丙基三乙氧基硅烷、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，所述基材为金属、塑料、织物、玻璃、电气组件、光学仪器或电气部件。
一种以上任意所述复合涂层的制备方法，包括：
提供基材，将基材置于等离子体反应腔室内，抽真空至20-250毫托，并通入惰性气体He、Ar、O 2或几种的混合气体；
将单体α、单体β和单体γ的蒸汽导入到反应腔室内，开启等离子体放电，形成等离子体聚合涂层Ⅰ。
可选的，所述方法还包括：将单体δ和单体ε的蒸汽导入到反应腔室内，开启等离子体放电，在涂层Ⅰ上形成等离子体聚合涂层Ⅱ。
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，脉冲频率为15Hz-60kHz,脉冲占空比为1％～85％，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以上任意所述的复合涂层。
本发明具体实施方式的复合涂层，将具有芳香环的不饱和酯类化合物和具有芳香基或环氧基的有机硅烷两种单体同时引入形成等离子体涂层，不饱和酯类化合物上带有芳香环，由于芳香环的稳定性好，能够使涂层具有较好的硬度以及耐腐蚀耐热耐温性能，同时疏水性提高，水溶解性降低，而且该单体含有酯基或羧基，可以形成氢键作用力，同时有机硅烷材料两端分别对有机物和无机物有较好的化学键结合力，故对基材有较好的附着结合效果。
本发明具体实施方式的复合涂层，将氟化物和有机硅烷两种单体同时引入形成等离子体涂层，有机硅烷在基材表面或者与防腐蚀层形成稳定的结合， 氟基团的加入，可提高疏水疏油性能，同时氟化物与硅烷间有较好的化学键结合，提高了涂层的耐磨性。
本发明具体实施方式的复合涂层，以具有芳香环的不饱和酯类单体、酯类偶联剂单体以及具有芳香基或环氧基的有机硅烷单体的等离子体形成的涂层作为里层，以含氟丙烯酸酯类单体和具有芳香基或环氧基的有机硅烷单体的等离子体形成的涂层作为外层，其形成的复合涂层具有优异的防腐性能的同时具有优异的耐磨性能。
附图说明
图1是实施例2对涂层后的Mg片和未涂层的Mg片进行电化学测试，得到的塔菲尔曲线图。
具体实施方式
本发明的具体实施方式提供一种复合涂层，所述复合涂层包括沉积于基材上的涂层Ⅰ，
所述涂层Ⅰ由包含单体α、单体β和单体γ的等离子体形成的等离子体聚合涂层；
所述单体α具有式(1-1)所示的结构，
Figure PCTCN2022124797-appb-000008
其中，Ar为带芳环的结构，T 1为-O-C(O)-或-C(O)-O-，X 1为连接部分，Y 1为连接部分，R 1、R 2和R 3分别独立的选自为氢原子、卤素原子、C 1-C 10的烷基或C 1-C 10的卤原子取代烷基；
所述单体β具有式(2-1)所示的结构，
Figure PCTCN2022124797-appb-000009
其中，S中含有一个以上的-O-C(O)-或-C(O)-O-，R 4、R 5、R 6、R 7、R 8和R 9分别独立的选自为氢原子、卤素原子、C 1-C 10的烷基或C 1-C 10的卤原子取代烷基；。
所述单体γ具有式(3-1)所示的结构，
Figure PCTCN2022124797-appb-000010
其中，R 10、R 11、R 12和R 13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的取代或未取代的芳香基，其中，R 10、R 11、R 12和R 13中的至少一个包含环氧基或为C 4-C 20的芳香基。
本发明具体实施方式的复合涂层，在一些具体实施方式中，所述复合涂层还包括涂层Ⅱ，所述涂层Ⅱ由所述涂层Ⅰ接触包含单体δ和单体ε的等离子体，从而在涂层Ⅰ上形成的等离子体聚合涂层；
所述单体δ具有式(4-1)所示的结构，
Figure PCTCN2022124797-appb-000011
其中，Z为连接部分，R 14、R 15和R 16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；
所述单体ε具有式(5-1)所示的结构，
Figure PCTCN2022124797-appb-000012
其中，R 17、R 18、R 19和R 20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的取代或未取代的芳香基，其中，R 17、R 18、R 19和R 20中的至少一个包含环氧基或为C 4-C 20的芳香基。
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Ar为芳环上带有取代基的苯环或杂芳环，在另一些具体实施方式中，所述Ar为芳环上不带有取代基的苯环或杂芳环。
本发明具体实施方式的复合涂层，所述X 1和Y 1为连接部分，X 1用于连接带芳环的结构Ar和酯键T 1，Y 1用于连接酯键T 1和饱和的碳碳双键，在一些具体实施方式中，所述X 1为下式(1-2)所示的结构，
*-X 11-X 12- *
       (1-2)
其中，X 11为连接键、-O-或-C(O)-，X 12为连接键、C 1-C 10的亚烷基或C 1-C 10的卤原子取代亚烷基；所述Y 1为连接键、C 1-C 10的亚烷基或C 1-C 10的卤原子取代亚烷基。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。
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R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 14、R 15和R 16分别独立的选自于氢原子或甲基。
本发明具体实施方式的复合涂层，在一些具体实施方式中，所述单体α具有式(1-3)所示的结构，
Figure PCTCN2022124797-appb-000013
其中，T 2为-O-C(O)-或-C(O)-O-，X 2为连接部分，用于连接苯环和酯键T 2，Y 2为连接部分，用于连接酯键T 2和碳碳双键；
R 21、R 22和R 23分别独立的选自为氢原子、卤素原子、C 1-C 10的烷基或C 1-C 10的卤原子取代烷基。所述烷基包括直链的烷基，例如甲基、乙基、丙基或丁基等，或含有支链的烷基，例如异丙基或异丁基等。
本发明具体实施方式的复合涂层，在一些具体实施方式中，式(1-3)所示的结构中，苯环上的两个取代基为对位取代，在另外一些实施例中也可以是邻位取代或间位取代。
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X 2为下式(1-4)所示的结构，
*-X 22-X 21- *
       (1-4)
其中，X 21为连接键、-O-或-C(O)-，X 22为连接键、C 1-C 10的亚烷基或C 1-C 10的卤原子取代亚烷基；所述Y 2为连接键、C 1-C 10的亚烷基或C 1-C 10的卤原子取代亚烷基。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。
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R 21、R 22和R 23分别独立的选自为氢原子或甲基。
本发明具体实施方式的复合涂层，作为具体的非限制性举例，所述单体α选自于丙烯酸-2-苯氧基乙酯(CAS号:48145-04-6)、丙烯酸苯酯(CAS号:937-41-7)、对苯二甲酸二烯丙酯(CAS号:1026-92-2)或甲基丙烯酸苯酯(CAS号:2177-70-0)中的至少一个。
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S中含 有-O-C(O)-或-C(O)-O-共两个，即S中含有两个-O-C(O)-、两个-C(O)-O-或-O-C(O)-或-C(O)-O-各一个；所述x在4以上，比如可以是4、5、6、7、8、9、10、11或12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S具有式(2-2)所示的结构，
Figure PCTCN2022124797-appb-000014
其中，R 24为C 2-C 10的亚烷基或C 2-C 10的卤原子取代亚烷基，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，y为0到10的整数。具体的为0、1、2、3、4、5、6、7、8、9或10。
本发明具体实施方式的复合涂层，作为具体的非限制性举例，所述单体β选自于二甲基丙烯酸1,4-丁二醇酯(CAS号：2082-81-7)、二甲基丙烯酸1,6-己二醇酯(CAS号：6606-59-3)、二甲基丙烯酸乙二醇酯(CAS号：97-90-5)、二甲基丙烯酸二乙二醇酯(CAS号：2358-84-1)、二甲基丙烯酸三乙二醇酯(CAS号：109-16-0)、二甲基丙烯酸四乙二醇酯(CAS号：109-17-1)、二甲基丙烯酸1,3-丁二醇酯(CAS号：1189-08-8)、二甲基丙烯酸新戊二醇酯(CAS号：1985-51-9)、甲基丙烯酸酐(CAS号:760-93-0)、二丙-2-烯基-2-亚甲基丁二酸酯、2-亚苄基丙二酸二丙-2-烯基酯(CAS号:52505-39-2)或二烯丙基丙二酸二乙酯(CAS号:3195-24-2)中的至少一个。
本发明具体实施方式的复合涂层，所述Z为连接部分，用于连接酯键全氟碳烷基，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复合涂层，在一些具体实施方式中，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，有利于提高涂层的疏水性。
本发明具体实施方式的复合涂层，作为具体的非限制性举例，所述单体δ选自于3-(全氟-5-甲基己基)-2-羟基丙基甲基丙烯酸酯(CAS号：16083-81-1)、2-(全氟癸基)乙基甲基丙烯酸酯(CAS号：2144-54-9)、2-(全氟己基)乙基甲基丙烯酸酯(CAS号：2144-53-8)、2-(全氟十二烷基)乙基丙烯酸酯(CAS号：27905-45-9)、2-全氟辛基丙烯酸乙酯(CAS号：27905-45-9)、1H,1H,2H,2H-全氟辛醇丙烯酸酯(CAS号：17527-29-6)、2-(全氟丁基)乙基丙烯酸酯(CAS号：52591-27-2)、(2H-全氟丙基)-2-丙烯酸酯(CAS号：59158-81-5)或(全氟环己基)甲基丙烯酸酯(CAS号：40677-94-9)中的一种或几种。
本发明具体实施方式的复合涂层，R 10、R 11、R 12和R 13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的取代或未取代的芳香基，其中，R 10、R 11、R 12和R 13中的至少一个包含环氧基或为C 4-C 20的芳香基；R 17、R 18、R 19和R 20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的取代或未取代的芳香基，其中，R 17、R 18、R 19和R 20中的至少一个包含环氧基或为C 4-C 20的芳香基；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；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；所述芳香基可以是芳基或杂芳基。
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R 10、R 11、R 12、R 13、R 17、R 18、R 19和R 20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复合涂层，在一些具体实施方式中，所述R 10、R 11、R 12、R 13、R 17、R 18、R 19和R 20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 10、R 11、R 12和R 13中的至少一个为C 6-C 20的芳基，R 17、R 18、R 19 和R 20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。在一些具体实施方式中更具体的，所述单体γ和单体ε分别独立的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)、苯基三乙烯基硅烷(CAS：18042-57-4)、甲基苯基二乙烯基硅烷、二甲基苯基乙烯基硅烷(CAS：1125-26-4)、甲氧基三苯基硅烷(CAS：1829-41-0)、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复合涂层，在一些具体实施方式中，所述R 10、R 11、R 12、R 13、R 17、R 18、R 19和R 20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 10、R 11、R 12和R 13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，R 17、R 18、R 19和R 20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。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。在一些具体实施方式中更具体的，所述单体γ和单体ε分别独立的选自于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)丙基甲基二乙氧基硅烷(CAS：2897-60-1)、3-(2,3-环氧丙氧)丙基三甲氧基硅烷(CAS：2530-83-8)、3-(2,3-环氧丙氧)丙基三乙氧基硅烷(CAS：2602-34-8)、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。
本发明具体实施方式的复合涂层，在一些具体实施方式中，所述基材为金属、塑料、织物、玻璃、电气组件、光学仪器或电气部件。具体地，所述金属具体例如可以是铁、镁、铝、铜或其合金，所述电气组件例如可以是印刷电路板(PCB)、电子产品或电子组装半成品等，所述电子产品例如电脑、智能手机、平板电脑、键盘、电子阅读器、可穿戴设备、显示器、耳机等，所述电气部件可以是、数据线(如Type-C数据线、USB数据线等)、透音网、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复合涂层，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，传统的防指纹镀膜工艺主要采用物理气相沉积工艺和湿法喷涂工艺，但这两种工艺相对来说价格比较昂贵且实验条件比较苛刻；本发明具体实施方式的等离子体聚合涂层，采用等离子体化学气相沉积法，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，大大提高了手机使用过程中的防水防油性能，同时具有优异的耐磨性能和防腐性能，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复合涂层，根据具体的单体情况，可以对单体α、单体β以及单体γ的比例进行调节，在一些具体实施方式中，所述单体α和单体β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，单体α与单体β的和与单体γ的摩尔比在1：10～10：1之间，具体例如可以是1：10、2：10、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、10：3、10：2、10：1等等。
本发明具体实施方式的复合涂层，根据具体的单体情况，可以对单体δ和单体ε的比例进行调节，在一些具体实施方式中，所述单体δ和单体ε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。
本发明具体实施方式的复合涂层，在一些具体实施方式中，所述涂层Ⅰ由单体α、单体β和单体γ的等离子体形成的等离子体聚合涂层，所述涂层Ⅱ由所述涂层Ⅰ接触单体δ和单体ε的等离子体，从而在涂层Ⅰ上形成的等离子体聚合涂层。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Ⅰ由单体α、单体β、单体γ和其它单体的等离子体形成，所述涂层Ⅱ由所述涂层Ⅰ接触单体δ、单体ε和其它单体的等离子体，从而在涂层Ⅰ上形成的等离子体聚合涂层。
本发明的具体实施方式还提供一种以上所述复合涂层的制备方法，包括：
提供基材，将基材置于等离子体反应腔室内，抽真空至20-250毫托，并通入惰性气体He、Ar、O 2或几种的混合气体；
将单体α、单体β和单体γ的蒸汽导入到反应腔室内，开启等离子体放电，形成等离子体聚合涂层Ⅰ。
进一步，所述方法还包括：将单体δ和单体ε的蒸汽导入到反应腔室内，开启等离子体放电，在涂层Ⅰ上形成等离子体聚合涂层Ⅱ。
本发明的具体实施方式的复合涂层制备方法，所述单体α、单体β、单体γ、单体δ、单体ε、涂层Ⅰ、涂层Ⅱ以及基材等的说明如前所述。
本发明具体实施方式的复合涂层制备方法，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复合涂层制备方法，在一些具体实施方式中，所述等离子体为脉冲等离子体，所述单体流量为50-3000ul/min，具体例如可以是100ul/min、200ul/min、300ul/min、400ul/min、500ul/min、1000ul/min、1500ul/min、2000ul/min、2500ul/min或3000ul/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；单体气化温度为50℃-180℃，具体例如可以是50℃、60℃、70℃、80℃、90℃、100℃、110℃、120℃、130℃、140℃、150℃、160℃、170℃或180℃等等，且是在真空条件下发生气化，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、40w、50w、60w、70w、80w、90w、100w、120W、140W、160W、180W、190W、200W、210W、220W、230W、240W、250W、260W、270W、280W、290W或300W等等；脉冲频率为15Hz-60kHz,具体例如可以是15Hz、20Hz、25Hz、30Hz、35Hz、40Hz、45Hz、50Hz、55Hz、60Hz、70Hz、80Hz、90Hz、100Hz、200Hz、300Hz、400Hz、500Hz、600Hz、700Hz、800Hz、900Hz、1kHz、2kHz、3kHz、4kHz、5kHz、10kHz、15kHz、20kHz、30kHz、40kHz、50kHz、60kHz等等；脉冲占空比为1％～85％，具体例如可以是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、2000s、3000s、4000s、5000s、6000s、7000s、8000s、9000s、10000s、15000s、20000s、25000s、30000s、36000s等等。
本发明具体实施方式的复合涂层制备方法，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复合涂层，在一些具体实施方式中，所述器件的部分表面或全部表面仅涂覆有上述的保护涂层。
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
耐盐雾测试：根据GB/T 2423.18-2000电工电子产品环境试验方法进行检测。
涂层厚度测试：使用美国Filmetrics F20-UV-薄膜厚度测量仪进行检测。
线路板耐摩擦测试：将线路板在耐磨试验机上进行摩擦，摩擦材料为无尘布，载荷200g，摩擦次数50次，转速40r/min，行程30mm；将摩擦后的线路板浸泡在水中，为其提供5V电压，用电脑检测电流，记录失效时间(电流＞0.6mA)。
手机屏片耐磨擦测试：将手机屏在耐磨试验机上进行摩擦，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。
电化学测试：上海辰华CHI660E C20704电化学分析仪，测试3.6％NaCl中性溶液中的极化曲线，测试条件，腐蚀电位为负600mv～正600mv，扫描速率0.00033mv/s,扫描时间600s。
实施例1
将线路板、Mg片、Fe片、手机屏片放置于等离子体腔室内，将腔室抽真空至60毫托，通入氦气，流量80sccm，开启等离子体放电，该预处理阶段放电功率为120W，持续放电800s；
往等离子体腔室内通入二丙烯酸-1,6-己二醇酯和甲基丙烯酸苯酯(质量比2:1)混合单体蒸汽，和苯基三甲氧基硅烷蒸汽，单体气化温度为180℃，流量分别均为300ul/min,开启等离子体放电，时间3000s，电源功率40W，频率45Hz，占空比35％，形成涂层Ⅰ；
然后往等离子体腔室内通入β-(3、4环氧环己基)-乙基三甲氧基硅烷蒸气和2-全氟辛基丙烯酸乙酯蒸气，单体气化温度为180℃，β-(3、4环氧环己基)-乙基三甲氧基硅烷流量为75μL/min，2-全氟辛基丙烯酸乙酯蒸气流量为75μL/min；开启等离子体放电，反应时间5400s，电源功率180W，频率45Hz，占空比1.5％，形成涂层Ⅱ；
放电结束后通入压缩空气，使腔体恢复常压，打开腔体，取出线路板、Mg片、Fe片、手机屏片，测试Mg片、Fe片涂层厚度以及进行耐盐雾测试结果列入表1中，测试线路板涂层厚度以及耐摩擦测试结果列入表2中，手机屏片耐磨擦测试结果列入表3中。
实施例2
将线路板、Mg片和Fe片放置于等离子体腔室内，将腔室抽真空至80毫托，通入氦气，流量140sccm，开启等离子体放电，该预处理阶段放电功率为180W，持续放电300s；
往等离子体腔室内通入二丙烯酸-1,6-己二醇酯和丙烯酸苯酯(质量比3:2)混合单体蒸汽，和二苯基二甲氧基硅烷蒸汽，单体气化温度为180℃，流量分别均为400ul/min,开启等离子体放电，时间3800s，电源功率37W，频率65Hz，占空比45％，形成涂层Ⅰ；
然后往等离子体腔室内通入苯基三甲氧基硅烷蒸气和1H,1H,2H,2H-全氟辛醇丙烯酸酯蒸气，单体气化温度为145℃，苯基三甲氧基硅烷蒸气流量为80μL/min，1H,1H,2H,2H-全氟辛醇丙烯酸酯蒸气流量为80μL/min；开启等离子体放电，反应时间6000s，电源功率180W，频率65Hz，占空比1％，形成涂层Ⅱ；
放电结束后通入压缩空气，使腔体恢复常压，打开腔体，取出线路板、Mg片和Fe片，测试Mg片和Fe片涂层厚度以及进行耐盐雾测试结果列入表1中，测试线路板涂层厚度以及耐摩擦测试结果列入表2中，对涂层后的Mg片和未涂层的Mg片进行电化学测试，得到塔菲尔曲线如附图1，对该曲线拟合得到其电化学参数结果列入表4中。
实施例3
将线路板、Mg片和Fe片放置于等离子体腔室内，将腔室抽真空至60毫托，通入氦气，流量80sccm，开启等离子体放电，该预处理阶段放电功率为120W，持续放电800s；
往等离子体腔室内通入二丙烯酸-1,6-己二醇酯和甲基丙烯酸苯酯(质量比2:1)混合单体蒸汽，和3-(2,3-环氧丙氧)丙基三甲氧基硅烷蒸汽，单体气化温度为180℃，流量分别均为300ul/min,开启等离子体放电，时间3000s，电源功率40W，频率45Hz，占空比35％，形成涂层Ⅰ；
然后往等离子体腔室内通入3-(2,3-环氧丙氧)丙基甲基二甲氧基硅烷蒸气和2-全氟辛基丙烯酸乙酯蒸气，单体气化温度为180℃，3-(2,3-环氧丙氧)丙基甲基二甲氧基硅烷蒸气流量为75μL/min，2-全氟辛基丙烯酸乙酯蒸气流量为75μL/min；开启等离子体放电，反应时间5400s，电源功率180W，频率45Hz， 占空比1.5％，形成涂层Ⅱ；
放电结束后通入压缩空气，使腔体恢复常压，打开腔体，取出线路板、Mg片和Fe片，测试Mg片和Fe片涂层厚度以及进行耐盐雾测试结果列入表1中，测试线路板涂层厚度以及耐摩擦测试结果列入表2中。
对比例1
将线路板、Mg片和Fe片放置于等离子体腔室内，将腔室抽真空至80毫托，通入氦气，流量140sccm，开启等离子体放电，该预处理阶段放电功率为180W，持续放电300s；
往等离子体腔室内通入二丙烯酸-1,6-己二醇酯和丙烯酸苯酯(质量比3:2)混合单体蒸汽，和γ-氨丙基三乙氧基硅烷蒸汽，单体气化温度为180℃，流量分别均为400ul/min,开启等离子体放电，时间3800s，电源功率37W，频率65Hz，占空比45％，形成涂层Ⅰ；
然后往等离子体腔室内通入苯基三甲氧基硅烷蒸气和1H,1H,2H,2H-全氟辛醇丙烯酸酯蒸气，单体气化温度为145℃，苯基三甲氧基硅烷蒸气流量为80μL/min，1H,1H,2H,2H-全氟辛醇丙烯酸酯蒸气流量为80μL/min；开启等离子体放电，反应时间6000s，电源功率180W，频率65Hz，占空比1％，形成涂层Ⅱ；
放电结束后通入压缩空气，使腔体恢复常压，打开腔体，取出线路板、Mg片和Fe片，测试Mg片和Fe片涂层厚度以及进行耐盐雾测试结果列入表1中，测试线路板涂层厚度以及耐摩擦测试结果列入表2中。
对比例2
将线路板、Mg片和Fe片放置于等离子体腔室内，将腔室抽真空至60毫托，通入氦气，流量80sccm，开启等离子体放电，该预处理阶段放电功率为120W，持续放电800s；
往等离子体腔室内通入二丙烯酸-1,6-己二醇酯和甲基丙烯酸苯酯(质量比2:1)混合单体蒸汽，单体气化温度为180℃，流量为600ul/min,开启等离子体放电，时间3000s，电源功率40W，频率45Hz，占空比35％，形成涂层Ⅰ；
然后往等离子体腔室内通入β-(3、4环氧环己基)-乙基三甲氧基硅烷蒸气和2-全氟辛基丙烯酸乙酯蒸气，单体气化温度为180℃，β-(3、4环氧环己基)-乙基三甲氧基硅烷流量为75μL/min，2-全氟辛基丙烯酸乙酯蒸气流量为75μL/min；开启等离子体放电，反应时间5400s，电源功率180W，频率45Hz，占空比1.5％，形成涂层Ⅱ；
放电结束后通入压缩空气，使腔体恢复常压，打开腔体，取出线路板、Mg片和Fe片，测试Mg片和Fe片涂层厚度以及进行耐盐雾测试结果列入表1中，测试线路板涂层厚度以及耐摩擦测试结果列入表2中。
对比例3
将线路板、Mg片和Fe片放置于等离子体腔室内，将腔室抽真空至60毫托，通入氦气，流量80sccm，开启等离子体放电，该预处理阶段放电功率为120W，持续放电800s；
往等离子体腔室内通入二丙烯酸-1,6-己二醇酯和甲基丙烯酸酯(质量比2:1)混合单体蒸汽，单体气化温度为180℃，流量为600ul/min,开启等离子体放电，时间3000s，电源功率40W，频率45Hz，占空比35％，形成涂层Ⅰ；
然后往等离子体腔室内通入β-(3、4环氧环己基)-乙基三甲氧基硅烷蒸气和2-全氟辛基丙烯酸乙酯蒸气，单体气化温度为180℃，β-(3、4环氧环己基)-乙基三甲氧基硅烷流量为75μL/min，2-全氟辛基丙烯酸乙酯蒸气流量为75μL/min；开启等离子体放电，反应时间5400s，电源功率180W，频率45Hz，占空比1.5％，形成涂层Ⅱ；
放电结束后通入压缩空气，使腔体恢复常压，打开腔体，取出线路板、Mg片和Fe片，测试Mg片和Fe片涂层厚度以及进行耐盐雾测试结果列入表1中，测试线路板涂层厚度以及耐摩擦测试结果列入表2中。
对比例4
将线路板、Mg片、Fe片放置于等离子体腔室内，将腔室抽真空至60毫托，通入氦气，流量80sccm，开启等离子体放电，该预处理阶段放电功率为120W，持续放电800s；
往等离子体腔室内通入β-(3、4环氧环己基)-乙基三甲氧基硅烷蒸气和2-全氟辛基丙烯酸乙酯蒸气，单体气化温度为180℃，β-(3、4环氧环己基)-乙基三甲氧基硅烷流量为75μL/min，2-全氟辛基丙烯酸乙酯蒸气流量为75μL/min；开启等离子体放电，反应时间16000s，电源功率180W，频率45Hz，占空比1.5％，形成涂层；
放电结束后通入压缩空气，使腔体恢复常压，打开腔体，取出线路板、Mg片、Fe片，测试Mg片、Fe片涂层厚度以及进行耐盐雾测试结果列入表1中，测试线路板涂层厚度以及耐摩擦测试结果列入表2中。
表1实施例1-3、对比例1-4耐盐雾测试结果
Figure PCTCN2022124797-appb-000015
表2实施例1-3、对比例1-4线路板耐摩擦测试结果
  基材 厚度(nm) 失效时间
实施例1 线路板 458 5h45min
实施例2 线路板 460 4h32min
实施例3 线路板 462 3h23min
对比例1 线路板 463 2h46min
对比例2 线路板 460 1h18min
对比例3 线路板 456 1h35min
对比例4 线路板 432 36min
表3实施例1手机屏片耐磨擦测试结果
Figure PCTCN2022124797-appb-000016
表4实施例2的电化学参数结果
Figure PCTCN2022124797-appb-000017
根据表1和表2的结果可知，相比于对比例1中，复合涂层以具有芳香环的不饱和酯类单体、酯类偶联剂单体以及一般的有机硅烷单体的等离子体形成的涂层作为里层，以含氟丙烯酸酯类单体和具有芳香基的有机硅烷单体的等离子体形成的涂层作为外层，对比例2中，复合涂层的里层不含有机硅烷单体，其以具有芳香环的不饱和酯类单体、酯类偶联剂单体的等离子体形 成的涂层作为里层，以含氟丙烯酸酯类单体和具有环氧基的有机硅烷单体的等离子体形成的涂层作为外层，对比例3中，复合涂层以不具有芳香环的不饱和酯类单体、酯类偶联剂单体以及具有芳香基的机硅烷单体的等离子体形成的涂层作为里层，以含氟丙烯酸酯类单体和具有环氧基的有机硅烷单体的等离子体形成的涂层作为外层，对比例4中，由含氟丙烯酸酯类单体和具有环氧基的有机硅烷单体的等离子形成的涂层，实施例1-3中复合涂层以具有芳香环的不饱和酯类单体、酯类偶联剂单体以及具有芳香基或环氧基的有机硅烷单体的等离子体形成的涂层作为里层，以含氟丙烯酸酯类单体和具有芳香基或环氧基的有机硅烷单体的等离子体形成的涂层作为外层，具有更优的耐盐雾测试结果和耐摩擦测试结果，表明实施例1-3的复合涂层具有最为优异的防腐性能和耐磨性能。
根据表3的结果可知，实施例1的复合涂层作为手机屏防护涂层，即使摩擦3000次，依然具有十分优异的防水防油性能。
根据表4的电化学参数结果可知，未涂层Mg片在3.6％NaCl中性溶液中的耐蚀性很差，发生了电化学腐蚀，阳极反应为镁的失电子溶解过程，阴极反应是水的得电子析氢过程。实验发现，未涂层Mg片自腐蚀电位为-1.385，具有复合涂层的Mg片的自腐蚀电位-1.101，腐蚀电位降低了26％，耐腐蚀性增强，同时镀有镀层的Mg片的电流密度9.569e -9A/cm 2，相对于未涂层Mg片电流密度降低了4个数量级。说明镀有涂层的Mg片防护性能较好。
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 (28)

  1. 一种复合涂层，其特征在于，所述复合涂层包括沉积于基材上的涂层Ⅰ，所述涂层Ⅰ由包含单体α、单体β和单体γ的等离子体形成的等离子体聚合涂层；
    所述单体α具有式(1-1)所示的结构，
    Figure PCTCN2022124797-appb-100001
    其中，Ar为带芳环的结构，T 1为-O-C(O)-或-C(O)-O-，X 1为连接部分，Y 1为连接部分，R 1、R 2和R 3分别独立的选自为氢原子、卤素原子、C 1-C 10的烷基或C 1-C 10的卤原子取代烷基；
    所述单体β具有式(2-1)所示的结构，
    Figure PCTCN2022124797-appb-100002
    其中，S中含有一个以上的-O-C(O)-或-C(O)-O-，R 4、R 5、R 6、R 7、R 8和R 9分别独立的选自为氢原子、卤素原子、C 1-C 10的烷基或C 1-C 10的卤原子取代烷基；
    所述单体γ具有式(3-1)所示的结构，
    Figure PCTCN2022124797-appb-100003
    Figure PCTCN2022124797-appb-100004
    其中，R 10、R 11、R 12和R 13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的取代或未取代的芳香基，其中，R 10、R 11、R 12和R 13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所述的复合涂层，其特征在于，所述R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8和R 9分别独立的选自于氢原子或甲基。
  3. 根据权利要求1所述的复合涂层，其特征在于，所述X 1为下式(1-2)所示的结构，
    *-X 11-X12-*
    (1-2)
    其中，X 11为连接键、-O-或-C(O)-，X 12为连接键、C 1-C 10的亚烷基或C 1-C 10的卤原子取代亚烷基；
    所述Y 1为连接键、C 1-C 10的亚烷基或C 1-C 10的卤原子取代亚烷基。
  4. 根据权利要求1所述的复合涂层，其特征在于，所述Ar为苯环结构或带有取代基的苯环结构。
  5. 根据权利要求4所述的复合涂层，其特征在于，所述单体α具有式(1-3)所示的结构，
    Figure PCTCN2022124797-appb-100005
    其中，T 2为-O-C(O)-或-C(O)-O-，X 2为连接部分，Y 2为连接部分；R 21、R 22和R 23分别独立的选自为氢原子、卤素原子、C 1-C 10的烷基或C 1-C 10的卤原子取代烷基。
  6. 根据权利要求5所述的复合涂层，其特征在于，所述X 2为下式(1-4)所示的结构，
    *-X 22-X 21-*
    (1-4)
    其中，X 21为连接键、-O-或-C(O)-，X 22为连接键、C 1-C 10的亚烷基或C 1-C 10的卤原子取代亚烷基；
    所述Y 2为连接键、C 1-C 10的亚烷基或C 1-C 10的卤原子取代亚烷基。
  7. 根据权利要求5所述的复合涂层，其特征在于，所述R 21、R 22和R 23分别独立的选自为氢原子或甲基。
  8. 根据权利要求1所述的复合涂层，其特征在于，所述单体α选自于丙烯酸-2-苯氧基乙酯、丙烯酸苯酯、对苯二甲酸二烯丙酯或甲基丙烯酸苯酯中的至少一个。
  9. 根据权利要求1所述的复合涂层，其特征在于，所述S中含有-O-C(O)-或-C(O)-O-共两个，x在4以上。
  10. 根据权利要求1所述的复合涂层，其特征在于，所述S具有式(2-2)所示的结构，
    Figure PCTCN2022124797-appb-100006
    其中，R 24为C 2-C 10的亚烷基或C 2-C 10的卤原子取代亚烷基，y为0到10的整数。
  11. 根据权利要求1所述的复合涂层，其特征在于，所述单体β选自于二甲基丙烯酸1,4-丁二醇酯、二甲基丙烯酸1,6-己二醇酯、二甲基丙烯酸乙二醇酯、二甲基丙烯酸二乙二醇酯、二甲基丙烯酸三乙二醇酯、二甲基丙烯酸四乙二醇酯、二甲基丙烯酸1,3-丁二醇酯、二甲基丙烯酸新戊二醇酯、甲基丙烯酸酐、二丙-2-烯基-2-亚甲基丁二酸酯、2-亚苄基丙二酸二丙-2-烯基酯或二烯丙基丙二酸二乙酯中的至少一个。
  12. 根据权利要求1所述的复合涂层，其特征在于，所述复合涂层还包括涂层Ⅱ，所述涂层Ⅱ由所述涂层Ⅰ接触包含单体δ和单体ε的等离子体，从而在涂层Ⅰ上形成的等离子体聚合涂层；
    所述单体δ具有式(4-1)所示的结构，
    Figure PCTCN2022124797-appb-100007
    其中，Z为连接部分，R 14、R 15和R 16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；
    所述单体ε具有式(5-1)所示的结构，
    Figure PCTCN2022124797-appb-100008
    其中，R 17、R 18、R 19和R 20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的取代或未取代的芳香基，其中，R 17、R 18、R 19和R 20中的至少一个包含环氧基或为C 4-C 20的芳香基。
  13. 根据权利要求12所述的复合涂层，其特征在于，所述R 14、R 15和R 16分别独立的选自于氢原子或甲基。
  14. 根据权利要求12所述的复合涂层，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。
  15. 根据权利要求12所述的复合涂层，其特征在于，所述单体δ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、(2H-全氟丙基)-2-丙烯酸酯或(全氟环己基)甲基丙烯酸酯中的 一种或几种。
  16. 根据权利要求1或12所述的复合涂层，其特征在于，所述R 10、R 11、R 12、R 13、R 17、R 18、R 19和R 20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。
  17. 根据权利要求16所述的复合涂层，其特征在于，所述R 10、R 11、R 12、R 13、R 17、R 18、R 19和R 20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 10、R 11、R 12和R 13中的至少一个为C 6-C 20的芳基，R 17、R 18、R 19和R 20中的至少一个为C 6-C 20的芳基。
  18. 根据权利要求17所述的复合涂层，其特征在于，所述芳基为苯基。
  19. 根据权利要求18所述的复合涂层，其特征在于，所述单体γ和单体ε分别独立的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、苯基三乙烯基硅烷、甲基苯基二乙烯基硅烷、二甲基苯基乙烯基硅烷、甲氧基三苯基硅烷、二苯基二甲氧基硅烷或苯基三甲氧基硅烷中的一种或几种。
  20. 根据权利要求16所述的复合涂层，其特征在于，所述R 10、R 11、R 12、R 13、R 17、R 18、R 19和R 20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 10、R 11、R 12和R 13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，R 17、R 18、R 19和R 20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。
  21. 根据权利要求20所述的复合涂层，其特征在于，所述环氧为脂环族环氧。
  22. 根据权利要求20所述的复合涂层，其特征在于，所述单体γ和单体ε分别独立的选自于3-(2,3-环氧丙氧)丙基甲基二甲氧基硅烷、3-(2,3-环氧丙氧)丙基甲基二乙氧基硅烷、3-(2,3-环氧丙氧)丙基三甲氧基硅烷、3-(2,3-环氧丙氧)丙基三乙氧基硅烷、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。
  23. 根据权利要求1所述的复合涂层，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。
  24. 一种权利要求1-23中任意一项所述复合涂层的制备方法，其特征在于，包括：
    提供基材，将基材置于等离子体反应腔室内，抽真空至20-250毫托，并通入惰性气体He、Ar、O 2或几种的混合气体；
    将单体α、单体β和单体γ的蒸汽导入到反应腔室内，开启等离子体放电，形成等离子体聚合涂层Ⅰ。
  25. 根据权利要求24所述复合涂层的制备方法，其特征在于，所述方法还包括：将单体δ和单体ε的蒸汽导入到反应腔室内，开启等离子体放电，在涂层Ⅰ上形成等离子体聚合涂层Ⅱ。
  26. 根据权利要求24或25所述复合涂层的制备方法，其特征在于，所述等离子体为脉冲等离子体。
  27. 根据权利要求26所述复合涂层的制备方法，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，脉冲频率为15Hz-60kHz,脉冲占空比为1％～85％，等离子放电时间为100s-36000s。
  28. 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1-23中任意一项所述的复合涂层。
PCT/CN2022/124797 2021-10-20 2022-10-12 一种复合涂层、制备方法及器件 Ceased WO2023066103A1 (zh)

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