WO2019037446A1 - 一种具有调制结构的高绝缘纳米防护涂层的制备方法 - Google Patents

一种具有调制结构的高绝缘纳米防护涂层的制备方法 Download PDF

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WO2019037446A1
WO2019037446A1 PCT/CN2018/082837 CN2018082837W WO2019037446A1 WO 2019037446 A1 WO2019037446 A1 WO 2019037446A1 CN 2018082837 W CN2018082837 W CN 2018082837W WO 2019037446 A1 WO2019037446 A1 WO 2019037446A1
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coating
monomer
discharge
vapor
reaction chamber
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PCT/CN2018/082837
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English (en)
French (fr)
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宗坚
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江苏菲沃泰纳米科技有限公司
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Priority to JP2020511261A priority Critical patent/JP6937430B2/ja
Priority to BR112020003338-3A priority patent/BR112020003338B1/pt
Priority to EP18849178.1A priority patent/EP3674438B1/en
Priority to KR1020207005150A priority patent/KR102373702B1/ko
Publication of WO2019037446A1 publication Critical patent/WO2019037446A1/zh
Priority to US16/798,131 priority patent/US11389825B2/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—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
    • C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • 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
    • B05D1/34—Applying different liquids or other fluent materials simultaneously
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/62—Plasma-deposition of organic layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/12—Organic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • 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
    • C23C16/448—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 characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • 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
    • C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • 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
    • C23C16/458—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 characterised by the method used for supporting substrates in the reaction chamber
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/515—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
    • 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
    • C23C16/517—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 a combination of discharges covered by two or more of groups C23C16/503 - C23C16/515
    • 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
    • C23C16/56—After-treatment

Definitions

  • the invention belongs to the technical field of plasma chemical vapor deposition, and in particular relates to a preparation method of a nano protective coating.
  • Anti-mold, anti-moist and anti-salt spray (referred to as three-proof) is an important problem that needs to be solved in the process of storage, transportation and use of electronic devices. Mold, salt spray and moisture often cause electronic devices to fail due to short circuits. Therefore, for the protective coating applied to the electronics industry, in addition to the excellent "three-proof" performance, it must also have good insulation.
  • the use of protective coatings to protect electronic products is an effective way to improve the service life of electronic products.
  • the liquid phase method usually adopts three anti-paints. After coating the electronic products, it uses thermal curing or photocuring to form a dense organic coating on the circuit board to protect the circuit boards and related equipment from environmental pollution. .
  • the three anti-paint has good resistance to high and low temperature; it forms a transparent protective film after curing, and has superior properties of insulation, moisture, leakage, shock, dust, corrosion, aging and corona resistance.
  • the liquid phase method will produce waste water, waste gas and waste liquid.
  • the solvent used will cause certain damage to the electronic device substrate itself.
  • the thickness is mostly several tens of micrometers, which is difficult to control at the nanometer level. For some electrons requiring heat dissipation and signal transmission. Device features will have an impact.
  • the gas phase method includes methods such as vapor deposition and plasma vapor deposition.
  • the most typical vapor deposition coating is a parylene coating, developed by Union Carbide Co. of the United States and widely used in electronic product protection.
  • the parylene coating is a p-xylene polymer that first heats para-xylene to 680 degrees Celsius to form an active para-xylene dimer. After the deposition chamber is lowered in temperature, the dimer is deposited in the electron. On the surface of the product, a polymer film is formed.
  • the parylene coating Since the paraxylene structure is highly symmetrical, the dipole moment is 0, and due to the presence of the benzene ring, the polymer molecule has a large free volume; and at the same time, due to the relatively large molecular weight of the polymer, the coating is dense. Due to the above characteristics, the parylene coating has low water, gas permeability and high barrier effect to achieve moisture, water, rust and acid and alkali corrosion resistance. This parylene is deposited under vacuum and can be used in applications where liquid coatings cannot be involved, such as high frequency circuits and very weak current systems. The thickness of the polymer film coating is the main reason for the protection failure of the para-xylene vapor-deposited conformal coating.
  • the polymer film coating of the printed circuit board component is prone to local rust failure at a thickness of 3 to 7 microns without affecting the high.
  • the coating thickness should be ⁇ 30 ⁇ m in the case of frequency dielectric loss.
  • Parylene coating requires high pretreatment of printed circuit boards that need protection, such as conductive components, signal transmission components, RF components, etc., in the vapor deposition of conformal coatings, it is necessary to pre-mask the circuit board components to avoid Affects component performance. This drawback has brought great limitations to the application of parylene coating.
  • Pyrene coatings have high cost of raw materials, harsh coating preparation conditions (high temperature, high vacuum requirements), low film formation rate, and are difficult to be widely used.
  • thick coatings tend to cause problems such as poor heat dissipation, signal rejection, and increased coating defects.
  • Plasma chemical vapor deposition is a technique in which a reactive gas is activated by a plasma to promote a chemical reaction on a surface of a substrate or a near surface to form a solid film.
  • Plasma chemical vapor deposition coatings have the following advantages:
  • the plasma polymerization film is stable in chemical and physical properties such as solvent resistance, chemical corrosion resistance, heat resistance, and abrasion resistance.
  • the plasma polymerization film has good adhesion to the substrate.
  • a uniform film can also be formed on the surface of the substrate having irregular irregularities.
  • the coating preparation temperature is low, and can be carried out under normal temperature conditions, thereby effectively avoiding damage to temperature sensitive devices.
  • the plasma process can not only prepare a coating having a thickness of a micron order but also can prepare an ultra-thin nano-scale coating.
  • the coating is highly configurable. Under plasma conditions, most of the organic monomers can be activated into highly active free radicals and form a coating on the surface of the electronic product.
  • the screening and design of the monomer dipole moment, chemical inertness, and free volume is an important strategy for obtaining a coating with good insulation and excellent protection in a thin condition.
  • the coating structure is highly controllable, and the composition and proportion of the monomer can be changed at any time, so that the coating has a special structure such as multilayer, gradient and modulation.
  • the performance is relatively simple.
  • the thickness must be increased, and the increase in thickness leads to a decrease in heat dissipation, signal transmission, and the like.
  • the present invention provides a method for preparing a high-insulation nano-protective coating having a modulation structure in order to solve the above technical problems.
  • the organic monomer with low dipole moment and high chemical inertness is screened, and the free volume and compactness of the coating are controlled by the polyfunctional monomer, so that the coating has high insulation and excellent protection at the same time.
  • the low dipole moment organic coating and the silicone coating preparation or the organic fluorocarbon coating are alternately prepared to form a low dipole moment-silicone/fluorocarbon modulation multilayer dense structure, composite modulation
  • the multi-layer structure is designed to achieve a significant increase in coating protection without sacrificing heat transfer and signal transmission.
  • the composition and structure of the coating are optimized by the design of the monomer and the optimization of the process parameters.
  • a nano-protective coating with a modulated structure can be designed.
  • the use of the interface between the layers prevents the longitudinal diffusion of corrosion; at the same time, due to the superlattice effect of the modulation of the nano-layered structure, the accumulation of dislocations between the layers makes the coating less likely to be broken down, and is resistant to underwater energization. The ability has been effectively improved.
  • This modulation structure coating has superior protection and insulation properties at the same thickness than existing coatings such as parylene. Protection and insulation can be achieved at lower thicknesses, thus solving many problems existing in the current coatings such as parylene, such as thick coating thickness, low production efficiency, poor heat dissipation, and signal blocking.
  • a method for preparing a high-insulation nano-protective coating having a modulation structure comprising: the following steps:
  • the substrate is placed in a reaction chamber of the nano-coating preparation device, and the reaction chamber is continuously evacuated, and the vacuum in the reaction chamber is pumped to 10 to 200 mTorr, and an inert gas of He, Ar or He and Ar is introduced. Mixing the gas, opening the moving mechanism to cause the substrate to move in the reaction chamber;
  • the monomer A vapor component comprises:
  • the monomer B vapor component comprises:
  • the monomer C vapor component comprises:
  • the passage of monomer A, monomer B and monomer C vapor is carried out by atomizing, volatilizing and introducing a monomer into a reaction chamber from a low pressure of 10 to 200 mTorr, the monomer A, single
  • the flow rate of the body B and the monomer C is 10 to 1000 ⁇ L / min;
  • Stop the plasma discharge continue to vacuum, keep the vacuum of the reaction chamber at 10 ⁇ 200 mTorr, and then pass air to an atmospheric pressure after 1 to 5 minutes to stop the movement of the substrate, and then take out the substrate;
  • stop the plasma discharge fill the reaction chamber with air or inert gas to a pressure of 2000-5000 mTorr, then evacuate to 10-200 mTorr, perform the above aeration and vacuum steps at least once, and pass air to a At atmospheric pressure, stop the movement of the substrate and then remove the substrate.
  • the substrate generates motion in the reaction chamber, and the substrate moves in the form of a linear reciprocating motion or a curved motion of the substrate relative to the reaction chamber, the curved motion including circular motion, elliptical motion, planetary motion, Curved motion of spherical motion or other irregular routes.
  • the substrate in the step (1) is a solid material
  • the solid material is an electronic product, an electrical component, an electronic assembly semi-finished product, a PCB board, a metal plate, a polytetrafluoroethylene plate or an electronic component, and the surface of the substrate
  • any interface can be exposed to water environment, mold environment, acid, alkaline solvent environment, acid, alkaline salt spray environment, acidic atmospheric environment, organic solvent soaking environment, cosmetic environment, sweat environment, Use in cold or hot cycle impact environment or wet heat alternating environment.
  • the reaction chamber is a rotating body chamber or a cubic chamber, the volume of which is 50-1000 L, the temperature of the reaction chamber is controlled at 30-60 ° C, and the flow rate of the inert gas is 5 ⁇ . 300sccm.
  • step (2) introducing a monomer A vapor, introducing a monomer B vapor or introducing a monomer C vapor, plasma discharge, performing chemical vapor deposition, and the plasma discharge process includes a low power continuous discharge during the deposition process. , pulse discharge or periodic discharge.
  • the plasma discharge process during the deposition process is a low power continuous discharge, specifically including the following deposition process at least once:
  • the deposition process includes a pretreatment stage and a coating stage.
  • the plasma discharge power in the pretreatment stage is 150-600 W
  • the continuous discharge time is 60-450 s
  • the plasma discharge power is adjusted to 10 to 150 W
  • the continuous discharge time is 600 to 3600 s. .
  • the plasma discharge process during the deposition is a pulse discharge, specifically including the following deposition process at least once:
  • the deposition process includes a pretreatment stage and a coating stage.
  • the plasma discharge power of the pretreatment stage is 150-600 W, and the continuous discharge time is 60-450 s, and then enters the coating stage.
  • the coating stage is pulse discharge, the power is 10 to 300 W, and the time is 600 s to 3600 s.
  • the frequency of the pulse discharge is 1 to 1000 Hz, and the duty ratio of the pulse is 1:1 to 1:500.
  • the plasma discharge process during the deposition process is a periodic alternating discharge, specifically including the following deposition process at least once:
  • the deposition process includes a pretreatment stage and a coating stage.
  • the plasma discharge power in the pretreatment stage is 150-600 W, and the continuous discharge time is 60-450 s, and then enters the coating stage.
  • the plasma in the coating stage is a periodic alternating discharge output with a power of 10 to 300 W.
  • the time is 600s ⁇ 3600s, the frequency conversion rate is 1-1000Hz, and the plasma cycle alternately changes.
  • the discharge output waveform is a sawtooth waveform, a sinusoidal waveform, a square wave waveform, a full-wave rectified waveform or a half-wave rectified waveform.
  • the low dipole moment organic monomer includes:
  • the monofunctional unsaturated fluorocarbon resin includes:
  • the silicone monomer containing a double bond, a Si—Cl, a Si—O—C, a Si—N—Si, a Si—O—Si structure or a ring structure includes:
  • Silicone monomer containing double bond structure allyl trimethoxy silane, vinyl triethoxy silane, vinyl trimethyl silane, 3-butenyl trimethyl silane, vinyl tributyl ketone fluorenyl Silane, tetramethyldivinyldisiloxane, 1,2,2-trifluorovinyltriphenylsilane;
  • Silicone monomer containing Si-Cl bond triphenylchlorosilane, methylvinyldichlorosilane, trifluoropropyltrichlorosilane, trifluoropropylmethyldichlorosilane, dimethylphenylchlorosilane , tributylchlorosilane, benzyldimethylchlorosilane;
  • Silicone monomer containing Si-OC structure tetramethoxysilane, trimethoxyhydrogensiloxane, n-octyltriethoxysilane, phenyltriethoxysilane, vinyltris(2-methoxy Ethyl ethoxy) silane, triethyl vinyl silane, hexaethylcyclotrisiloxane, 3-(methacryloyloxy)propyl trimethoxy silane, phenyl tris(trimethyl siloxane group Silane, diphenyldiethoxysilane, dodecyltrimethoxysilane, n-octyltriethoxysilane, dimethoxysilane, 3-chloropropyltrimethoxysilane;
  • Silicone monomer containing Si-N-Si or Si-O-Si structure hexamethyldisilazide, hexamethylcyclotrisilylamino, hexamethyldisilazane, hexamethyldisiloxane;
  • Silicone monomer containing cyclic structure hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, hexaphenylcyclotrisiloxane, decamethylcyclopentasiloxane, octaphenyl ring Tetrasiloxane, triphenylhydroxysilane, diphenyldihydroxysilane, bis(tritylsilyl) chromate, trifluoropropylmethylcyclotrisiloxane, 2,2,4,4 -tetramethyl-6,6,8,8-tetraphenylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, 3-glycidoxypropyltriethoxysilane, ⁇ - glycidyloxypropyltrimethoxysilane;
  • the polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives include:
  • the plasma discharge mode is radio frequency discharge, microwave discharge, intermediate frequency discharge, high frequency discharge, and electric spark discharge, and the waveforms of the high frequency discharge and the intermediate frequency discharge are sinusoidal or bipolar pulses, and the radio frequency is A plasma is a plasma generated by discharge of a high-frequency electromagnetic field.
  • the microwave method utilizes the energy of the microwave to excite the plasma, and has the advantages of high energy utilization efficiency.
  • the electrodeless discharge and the plasma are pure, it is an excellent method for high-quality, high-rate, large-area preparation.
  • the motion characteristics of the substrate and the plasma discharge energy are combined.
  • the substrate generates motion, improves the deposition efficiency of the coating, and improves the uniformity and compactness of the coating thickness.
  • the prepared coating has insulation, waterproof and moisture proof, anti-mold, acid and alkaline solvents, acid and alkali salt spray, acid atmosphere, organic solvent immersion, cosmetics resistance, sweat resistance, cold and heat cycle impact resistance (-40 °C ⁇ +75 ° C), resistance to heat and humidity (humidity 75% ⁇ 95%) and other characteristics.
  • the coating thickness is between 1 and 1000 nm, and the influence on the RF communication signal in the range of 10M to 8G is less than 5%.
  • the plasma chemical vapor deposition method is more environmentally friendly than the liquid phase three-coating coating method; and the deposition temperature is lower, the speed is faster, and the coating structure and composition are controllable compared to the vapor deposition parylene method. Strong, the monomer is highly selective.
  • the substrate moves in the reaction chamber, so that the coating thickness of the substrate at different positions tends to be uniform, which solves the problem that the thickness of the coating on the surface of the substrate is not uniform due to the difference in monomer density in different regions of the reaction chamber.
  • the amount of chemical monomer raw materials used in monomer steam is only 10% to 15% of the amount in other prior art, thereby reducing emissions of exhaust gas, making it more environmentally friendly and improving actual production efficiency. It has great significance.
  • the present invention screens organic monomers having low dipole moment and high chemical inertness, and controls the free volume and compactness of the coating by the polyfunctional monomer, so that the coating has high insulation and excellent protection at the same time.
  • the present invention selects a benzene ring having a high symmetry and a benzene derivative or a perfluoro compound as a monomer, and the polymer after polymerization is symmetrical or each carbon atom is coated with a large amount of fluorine atoms, and the polarity is low, and the dielectric is low.
  • the constant is very low, less than 2.7, and the insulation is high;
  • the formed polymer has excellent chemical stability
  • the invention adopts a method of alternately performing low dipole moment organic coating and silicone coating preparation or organic fluorocarbon coating to form a low dipole moment-silicone/fluorocarbon modulation multilayer dense structure, which can be reduced
  • the stress of the coating increases the toughness of the coating.
  • the corrosive medium corrodes the coating. When the transverse interface is encountered, the corrosion will develop laterally.
  • the present invention employs plasma chemical vapor deposition to obtain a nano-protective coating having a modulated structure by controlling the structure of the monomer and the coating.
  • This coating has the following advantages: each cycle consists of a layer of nano-scale low dipole moment and nano-scale silicone coating or organic fluorocarbon coating, the total thickness of the coating is controlled between 20nm-10 ⁇ m; hardness Controllable between HB-4H; excellent insulation performance, underwater resistance and low surface energy; excellent three-proof performance.
  • the method of the invention is more than a single long-time coating, and the obtained coating has a bonding strength and a density which are at least 40%-50% and 35%-50%, respectively, and the underwater electric resistance is increased by 40%-50%. .
  • the modulation structure coating obtained by alternately circulating the cycle has excellent performance and strong practicability.
  • General plasma polymerization uses a monofunctional hydrocarbon-hydrogen organic compound monomer to obtain a coating having a certain cross-linking structure.
  • the crosslinked structure is formed by a plurality of active sites formed by chain scission of a monomer during plasma discharge by cross-linking.
  • this crosslinked structure is relatively loose, contains more linear components, and is resistant to solution penetration and solubility.
  • the silicon-bonded functional groups in the silicone monomer can undergo a condensation reaction with each other, and therefore, a three-dimensional network can occur between the monomer and the monomer.
  • Cross-linking can further improve the compactness, wear resistance and corrosion resistance of the coating.
  • the hardness of the silicone coating of the same thickness is 1-2 grades higher than that of the conventional coating, and the salt spray resistance is increased by 30-50%.
  • portable device keyboard has small and light features, commonly used in computers, mobile phones and other equipment. It makes it easy for users to work on the journey. However, when it encounters the contamination of common liquids, such as the accidental overturn of the water cup, the soaking of rain and sweat, the inside of the keyboard is easily short-circuited and damaged. After coating with this type of nano-coating, it can ensure that the surface of the keyboard is easy to clean and function properly after being exposed to water, so that the keyboard can adapt to a more severe environment.
  • LED display has product promotion, store decoration, lighting, warning and other purposes. Some of its uses need to face the harsh environment of rain or dust, such as the rainy days, the mall's open-air LED advertising screen, road warning lights, LED display control panel in the production workshop, these harsh environments lead to LED screen failure, and easy to accumulate dust, It is difficult to clean, and after using the nano-coating, the above problems can be effectively solved.
  • fingerprint lock is a smart lock, which integrates computer information technology, electronic technology, mechanical technology and modern hardware technology, is widely used in public security criminal investigation and judicial field. However, after it meets water, its internal circuit is short-circuited, difficult to repair, and requires violent de-locking. This coating can be used to avoid this problem.
  • Some sensors need to work in a liquid environment, such as water pressure, oil pressure sensors, and sensors used in underwater operation equipment, as well as sensors that often encounter water in the working environment. These sensors use this coating. After the layer, it can guarantee that the sensor will not malfunction due to the liquid invading the internal structure of the mechanical device.
  • the silicone nano-coating prepared by the method can also be applied to the following different environments and related products:
  • Acid and alkaline solvents, acid and alkali salt spray, acid resistant atmosphere are acids and alkaline solvents, acid and alkali salt spray, acid resistant atmosphere:
  • 1 such as paraffin, olefin, alcohol, aldehyde, amine, ester, ether, ketone, aromatic hydrocarbon, hydrogenated hydrocarbon, terpene olefin, halogenated hydrocarbon, heterocyclic compound, nitrogen-containing compound and sulfur compound solvent; 2 cosmetic packaging container ; 3 fingerprint lock, headphones.
  • Resistance to cold and heat cycle (-40 ° C ⁇ +75 ° C), resistance to heat and humidity (humidity 75% ⁇ 95%): electrical, electronic, automotive electrical, such as aviation, automotive, home appliances, scientific research and other fields of equipment.
  • a method for preparing a high-insulation nano-protective coating having a modulation structure comprising the steps of:
  • the substrate is placed in a reaction chamber of the nano-coating preparation device, the reaction chamber is closed, and the reaction chamber is continuously evacuated, and the vacuum in the reaction chamber is pumped to 10 mTorr, and an inert gas Ar is introduced to open the moving mechanism. , causing the substrate to generate motion in the reaction chamber;
  • the substrate in the step (1) is a solid material, the solid material is a bulk aluminum material and a PCB board, and the surface of the substrate is prepared to be exposed to cold and heat after being subjected to a cold and heat resistant cyclic impact coating. In a loop test environment.
  • the reaction chamber is a rotating body chamber
  • the volume of the reaction chamber is 50 L
  • the temperature of the reaction chamber is controlled at 30 ° C
  • the flow rate of the inert gas is 5 sccm.
  • the substrate moves in the reaction chamber, and the substrate moves in the form of a circular motion of the substrate relative to the reaction chamber at a rotation speed of 10 rpm.
  • the monomer A vapor component comprises:
  • the low dipole moment organic monomer is: 1,8-diiodo perfluorooctane,
  • the two polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives are: 1,3-butadiene, ethoxylated trimethylolpropane triacrylate;
  • the monomer B vapor component comprises:
  • the monofunctional unsaturated fluorocarbon resin is: 2-(perfluorododecyl)ethyl acrylate
  • the three polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives are: 1,4-pentadiene, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate;
  • the flow of the monomer A and the monomer B is carried out by atomizing and volatilizing the monomer through a feed pump and introducing into the reaction chamber from a low pressure of 10 mTorr, wherein the flow rates of the monomer A and the monomer B are both 10 ⁇ L/min;
  • the monomer A vapor or the monomer B vapor is introduced, the plasma is discharged, and the chemical vapor deposition is performed.
  • the plasma discharge process is a small power continuous discharge, specifically including the following deposition process. :
  • the deposition process includes the pretreatment stage and the coating stage.
  • the plasma discharge power of the pretreatment stage is 150W, the discharge time is 450s, and then enters the coating stage.
  • the plasma discharge power is adjusted to 10W and the continuous discharge time is 3600s.
  • the plasma discharge mode is radio frequency discharge
  • the plasma discharge is stopped, the vacuum is continuously applied, and the vacuum of the reaction chamber is maintained at 10 mTorr. After 1 min, air is introduced to an atmospheric pressure, and then the substrate is taken out.
  • the dielectric constant of the coating obtained by the above process is 2.73. After coating the aluminum material and PCB board, the cold and thermal cycle impact test results are as follows:
  • a method for preparing a high-insulation nano-protective coating having a modulation structure comprising the steps of:
  • the substrate in the step (1) is a solid material, and the solid material is a bulk aluminum material, and any interface of the surface of the substrate after the preparation of the moisture-resistant heat alternating coating can be exposed to the damp heat test environment.
  • the reaction chamber is a cubic chamber, the volume of the reaction chamber is 270 L, the temperature of the reaction chamber is controlled at 42 ° C, and the flow rate of the inert gas is 18 sccm.
  • the substrate is subjected to planetary motion, the revolution speed is 4 rpm, and the rotation speed is 10 rpm.
  • the monomer A vapor is introduced into the reaction chamber to a vacuum of 70 mTorr, plasma discharge is started, chemical vapor deposition is performed, the monomer A vapor is stopped, the monomer C vapor is introduced, and the plasma discharge is continued. Chemical vapor deposition, stopping the passage of monomer C vapor;
  • the monomer A vapor component comprises:
  • the three low dipole moment organic monomers are: polydimethylsiloxane having a molecular weight of 50,000, decafluorobiphenyl ketone, and hexafluoropropylene;
  • the polyfunctional unsaturated hydrocarbon and hydrocarbon derivative are: ethylene glycol diacrylate;
  • the monomer C vapor component comprises:
  • the organosilicon monomer containing a double bond structure is: vinyl tributol sulfonyl silane,
  • the four polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives are: isoprene, 1,4-pentadiene, tripropylene glycol diacrylate, diethylene glycol divinyl ether;
  • the flow of the monomer A and the monomer C is carried out by atomizing and volatilizing the monomer through a feed pump and introducing the reaction chamber into the reaction chamber by a low pressure of 30 mTorr, wherein the flow rates of the monomer A and the monomer C are both 85 ⁇ L/min;
  • a monomer A vapor or a monomer C vapor is introduced, a plasma discharge is performed, and a chemical vapor deposition is performed.
  • the plasma discharge process is a small power continuous discharge, specifically including the following deposition process 5 Times:
  • the deposition process includes a pretreatment stage and a coating stage.
  • the plasma discharge power of the pretreatment stage is 600 W, the discharge time is 60 s, and then enters the coating stage.
  • the plasma discharge power is adjusted to 150 W and the continuous discharge time is 600 s.
  • the plasma discharge mode is microwave discharge
  • the plasma discharge is stopped, the vacuum is continuously applied, and the vacuum of the reaction chamber is maintained at 60 mTorr. After 2 minutes, the air is introduced to an atmospheric pressure, and then the substrate is taken out.
  • the dielectric constant of the coating obtained by the above process is 2.45.
  • the thermal and thermal cycling impact test results are as follows:
  • a method for preparing a high-insulation nano-protective coating having a modulation structure comprising the steps of:
  • the substrate in the step (1) is a solid material
  • the solid material is a bulk polytetrafluoroethylene plate and an electrical component
  • any interface of the block-shaped polytetrafluoroethylene plate is exposed after the preparation of the anti-fungal coating.
  • the surface of the electrical component can be exposed to the environment described in the international industrial waterproof rating standard IPX7 after the waterproof and electrical breakdown coating is prepared.
  • the reaction chamber is a rotating body chamber
  • the volume of the reaction chamber is 580 L
  • the temperature of the reaction chamber is controlled at 53 ° C
  • the flow rate of the inert gas is 65 sccm.
  • the substrate was subjected to a circular motion at a rotation speed of 12 rpm.
  • the monomer A vapor component comprises:
  • the four low dipole moment organic monomers are: toluene, ⁇ -methyl styrene, dimethyl siloxane, decafluorobiphenyl ketone,
  • the two polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives are: isoprene, neopentyl glycol diacrylate;
  • the monomer C vapor component comprises:
  • the five Si-Cl-containing silicone monomers are: triphenylchlorosilane, trifluoropropylmethyldichlorosilane, dimethylphenylchlorosilane, tributylchlorosilane, benzyl dimethyl Chlorosilane,
  • the two polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives are: polyethylene glycol diacrylate, 1,6-hexanediol diacrylate;
  • the flow of the monomer A and the monomer C is carried out by atomizing and volatilizing the monomer through a feed pump and introducing into the reaction chamber from a low pressure of 80 mTorr, wherein the flow rates of the monomer A and the monomer C are both 440 ⁇ L/min;
  • a monomer A vapor is introduced or a monomer C vapor is introduced, and a plasma discharge is performed to perform chemical vapor deposition.
  • the plasma discharge process is a pulse discharge during the deposition process, and specifically includes the following deposition process:
  • the deposition process includes pretreatment stage and coating stage.
  • the plasma discharge power of the pretreatment stage is 150W, the discharge time is 450s, and then enters the coating stage.
  • the coating stage is pulse discharge, power 10W, time 3600s, pulse discharge frequency is 1HZ, pulse The duty cycle is 1:500;
  • the plasma discharge mode is an electric spark discharge
  • the plasma discharge is stopped, the vacuum is continuously applied, the vacuum of the reaction chamber is maintained at 100 mTorr, and after 3 minutes, air is introduced to an atmospheric pressure, and then the substrate is taken out.
  • the dielectric constant of the coating obtained by the above process was 2.46, and the GJB150.10A-2009 mold test result after coating the polytetrafluoroethylene plate:
  • IPX 7 waterproof rating test (underwater 1m water immersion test 30min) results:
  • a method for preparing a high-insulation nano-protective coating having a modulation structure comprising the steps of:
  • the substrate in the step (1) is a solid material
  • the solid material is a bulk polytetrafluoroethylene plate and an electrical component
  • any interface of the block-shaped polytetrafluoroethylene plate is exposed after the preparation of the anti-fungal coating.
  • the surface of the electrical component can be exposed to the environment described in the international industrial waterproof rating standard IPX7 after the waterproof and electrical breakdown coating is prepared.
  • the volume of the reaction chamber in the step (1) was 640 L, the temperature of the reaction chamber was controlled at 54 ° C, and the flow rate of the inert gas was 240 sccm.
  • the substrate was linearly reciprocated at a moving speed of 23 mm/min.
  • the monomer A vapor component comprises:
  • the five low dipole moment organic monomers are: p-xylene, 1H, 1H-perfluorooctylamine, 2-(perfluorooctyl)ethyl methacrylate, 1,1,2,2- Tetrahydroperfluorohexyl iodide, 2,4,6-tris(perfluoroheptyl)-1,3,5-triazine,
  • the three polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives are: isoprene, tripropylene glycol diacrylate, polyethylene glycol diacrylate;
  • the monomer B vapor component comprises:
  • the four monofunctional unsaturated fluorocarbon resins are: 2-(perfluorobutyl)ethyl acrylate, (perfluorocyclohexyl) methacrylate, 3,3,3-trifluoro-1-propene Alkyne, 4-ethynyl trifluorotoluene,
  • the four polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives are: isoprene, 1,4-pentadiene, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate;
  • the flow of the monomer A and the monomer B is carried out by atomizing and volatilizing the monomer through a feed pump and introducing the reaction chamber into the reaction chamber by a low pressure of 100 mTorr, wherein the flow rates of the monomer A and the monomer B are both 1000 ⁇ L/min;
  • a monomer A vapor is introduced or a monomer B vapor is introduced, and a plasma discharge is performed to perform chemical vapor deposition.
  • the plasma discharge process is a pulse discharge during the deposition process, specifically including the following deposition process seven times. :
  • the deposition process includes pretreatment stage and coating stage.
  • the plasma discharge power of the pretreatment stage is 600W, the discharge time is 60s, and then enters the coating stage.
  • the coating stage is pulse discharge, power 300W, time 600s, pulse discharge frequency is 1000HZ, pulse The duty ratio is 1:1;
  • the plasma discharge mode is a high frequency discharge, and the waveform of the high frequency discharge is a sine;
  • the dielectric constant of the coating obtained by the above process was 2.48. After the coating of the polytetrafluoroethylene plate, the GJB150.10A-2009 mold test results:
  • IPX 7 waterproof rating test (underwater 1m water immersion test 30min) results:
  • a method for preparing a high-insulation nano-protective coating having a modulation structure comprising the steps of:
  • the substrate in the step (1) is a solid material, and the solid material is a bulk aluminum material, and any interface of the substrate surface can be exposed to an acid or alkali test environment after preparing an acid-proof and alkaline environment coating. .
  • the volume of the reaction chamber in the step (1) was 1000 L, the temperature of the reaction chamber was controlled at 60 ° C, and the flow rate of the inert gas was 300 sccm.
  • the substrate was subjected to a curve reciprocating motion at a speed of 50 mm/min.
  • the monomer A vapor is introduced into the reaction chamber to a vacuum of 300 mTorr, plasma discharge is started, chemical vapor deposition is performed, the monomer A vapor is stopped, the monomer C vapor is introduced, and the plasma discharge is continued. Chemical vapor deposition, stopping the passage of monomer C vapor;
  • the monomer A vapor component comprises:
  • the six low dipole moment organic monomers are: benzene, ⁇ -methylstyrene, dimethylsiloxane, allylbenzene, 2-(perfluorobutyl)ethyl methacrylate, 1, 1,2,2-tetrahydroperfluorohexyl iodide,
  • the three polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives are: 1,4-pentadiene, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate;
  • the monomer C vapor component comprises:
  • the four Si-OC structure-containing silicone monomers are: trimethoxyhydrogensiloxane, n-octyltriethoxysilane, triethylvinylsilane, 3-(methacryloyloxy)propane Trimethoxysilane,
  • the three polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives are: 1,4-pentadiene, ethoxylated trimethylolpropane triacrylate, polyethylene glycol diacrylate;
  • the flow of the monomer A and the monomer C is carried out by atomizing and volatilizing the monomer through a feed pump and introducing into the reaction chamber from a low pressure of 200 mTorr, wherein the flow rates of the monomer A and the monomer C are both 780 ⁇ L/min;
  • a monomer A vapor is introduced or a monomer C vapor is introduced, and a plasma discharge is performed to perform chemical vapor deposition.
  • the plasma discharge process is alternately discharged periodically, specifically including the following deposition process. :
  • the deposition process includes the pretreatment stage and the coating stage.
  • the plasma discharge power of the pretreatment stage is 150W
  • the continuous discharge time is 450s
  • the coating stage is the periodic alternating discharge output, power 10W, time 3600s, alternating frequency At 1 Hz, the plasma cycle alternates with the discharge output waveform as a sawtooth waveform.
  • the plasma discharge mode is an intermediate frequency discharge, and the waveform of the intermediate frequency discharge is a bipolar pulse;
  • the substrate obtained after the removal of the substrate can be obtained by the above process and the aluminum material after the coating, and the test results are as follows:
  • a method for preparing a high-insulation nano-protective coating having a modulation structure comprising the steps of:
  • the substrate is a solid material, which is a bulk aluminum material and an electrical component, and any interface of the substrate surface after the preparation of the high insulating coating can be exposed to the organic solvent test environment.
  • the volume of the reaction chamber in the step (1) was 400 L, the temperature of the reaction chamber was controlled at 40 ° C, and the flow rate of the inert gas was 150 sccm.
  • the substrate was subjected to a curve reciprocating motion at a speed of 30 mm/min.
  • the monomer A vapor is introduced into the reaction chamber to a vacuum of 230 mTorr, plasma discharge is started, chemical vapor deposition is performed, the monomer A vapor is stopped, the monomer C vapor is introduced, and the plasma discharge is continued. Chemical vapor deposition, stopping the passage of monomer C vapor;
  • the monomer A vapor component comprises:
  • the five low dipole moment organic monomers are: allylbenzene, decafluorobiphenyl ketone, hexafluoropropylene, 1H, 1H-perfluorooctylamine, perfluorooctyl iodine,
  • the four polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives are: 1,4-pentadiene, ethoxylated trimethylolpropane triacrylate, polyethylene glycol diacrylate, 1,6- Hexanediol diacrylate;
  • the monomer C vapor component comprises:
  • silicone monomers containing a cyclic structure hexaphenylcyclotrisiloxane, octaphenylcyclotetrasiloxane, diphenyldihydroxysilane, bis(tritylsilyl) chromate Ester, trifluoropropylmethylcyclotrisiloxane, 2,2,4,4-tetramethyl-6,6,8,8-tetraphenylcyclotetrasiloxane,
  • the four polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives are: 1,3-butadiene, isoprene, ethoxylated trimethylolpropane triacrylate, ethylene glycol diacrylate;
  • the flow of the monomer A and the monomer C is carried out by atomizing and volatilizing the monomer through a feed pump and introducing into the reaction chamber from a low pressure of 160 mTorr, wherein the flow rates of the monomer A and the monomer C are both 460 ⁇ L/min;
  • a monomer A vapor is introduced or a monomer C vapor is introduced, and a plasma discharge is performed to perform chemical vapor deposition.
  • the plasma discharge process is periodically alternately discharged, specifically including the following deposition process. Times:
  • the deposition process includes the pretreatment stage and the coating stage.
  • the plasma discharge power of the pretreatment stage is 600W
  • the discharge time is 60s
  • the plasma in the coating stage is the cycle alternating discharge output, power 300W, time 600s, alternating frequency At 1000 Hz, the plasma cycle alternately changes the discharge output waveform to a half-wave rectified waveform.
  • the plasma discharge mode is microwave discharge

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Abstract

一种具有调制结构的高绝缘纳米防护涂层的制备方法，属于等离子体技术领域，该方法中，将反应腔室抽真空度，并通入惰性气体，使基材产生运动，采用交替进行低偶极矩有机物涂层和有机硅涂层制备或有机氟碳涂层制备的方式，形成低偶极矩-有机硅/氟碳的调制多层致密结构，可降低涂层的应力，提高涂层的韧性；同时由于低偶极矩-有机硅/氟碳之间存在横向界面，腐蚀介质对涂层进行腐蚀过程中，遇到横向界面，则腐蚀会往横向发展，而不容易形成贯穿涂层的纵向腐蚀，避免腐蚀介质透过涂层而腐蚀被保护的材料与器件；同时，由于调制纳米层状结构的超晶格效应，层层之间位错的堆积，使得涂层更不容易被击穿，耐水下通电能力得到有效提高。

Description

一种具有调制结构的高绝缘纳米防护涂层的制备方法 技术领域
本发明属于等离子体化学气相沉积技术领域，具体涉及到一种纳米防护涂层的制备方法。
背景技术
防霉菌、防潮湿、防盐雾(简称三防)是电子器件在存储、运输及使用过程中需要解决的重要问题。而霉菌、盐雾和潮湿通常导致电子器件由于短路而失效。因此，对于应用于电子行业的防护涂层，除了具有优异的“三防”性能，还必须有良好的绝缘性。
目前，采用防护涂层对电子产品进行防护，是提高电子产品使用寿命的有效方法。获得防护涂层通常有两种方法，液相法和气相法。液相法通常采用三防漆，对电子产品进行涂敷后，利用热固化或光固化，在电路板上形成一层致密有机涂层，用于保护线路板及其相关设备免受环境的侵蚀。三防漆具有良好的耐高低温性能；其固化后成一层透明保护膜，具有优越的绝缘、防潮、防漏电、防震、防尘、防腐蚀、防老化、耐电晕等性能。但液相方法会产生废水、废气和废液，使用的溶剂会对电子器件基板本身产生一定损伤，此外其厚度大多为几十微米，难以控制在纳米级别，对于一些需要散热和信号传输的电子器件功能会有一定影响。
气相法则包括蒸镀、等离子体气相沉积等方法。最典型的蒸镀涂层为派瑞林涂层，由美国Union Carbide Co.开发并大量应用在电子产品防护当中。派瑞林涂层是一种对二甲苯的聚合物，先将对二甲苯加热到680摄氏度，形成具有活性对二甲苯二聚体，在沉积腔降低温度后，这种二聚体沉积在电子产品表面，形成聚合物薄膜。由于对二甲苯结构高度对称，偶极矩为0，且由于苯环的存在，聚合物分子具有较大的自由体积；同时由于聚合物分子量相对较大，使得涂层致密性高。由于以上特征，派瑞林涂层具有低水、气体渗透性、高屏障效果能够达到防潮、防水、防锈、抗酸碱腐蚀的作用。这种聚对二甲苯是在真空状态下沉积产生，可以应用在液态涂料所无法涉及的领域如高频电路、极弱电流系统的保护。聚合物薄膜涂层厚度是影响聚对二甲苯气相沉积敷形涂层防护失效的主要原因，印制电路板组件聚合物薄膜涂层在3～7微米厚度易发生局部锈蚀失效，在不影响高频介电损耗情况下涂层厚度应≥30微米。派瑞林涂层对于需要防护的印刷线路板的预处理要求较高，例如导电组件、信号传输组件、射频组件等，在气相沉积敷形涂层时需要对线路板组件做遮蔽预处理，避免对组件性能造成影响。这一弊端给派瑞林涂层的应用带来了极大限制。派瑞林涂层制备原料成本高、涂层制备条件苛刻(高温、高真空度要求)、成膜速率低，难以广泛应用。此外，厚涂层易导致 散热差、信号阻隔、涂层缺陷增多等问题。
针对以上问题，开发一种环保、绝缘性好，在涂层较薄情况下具有优异防护性能的涂层及制备方法，具有重要的应用价值。
等离子体化学气相沉积(plasma chemical vapor deposition,PCVD)是一种用等离子体激活反应气体，促进在基体表面或近表面空间进行化学反应，生成固态膜的技术。等离子体化学气相沉积法涂层具有以下优点：
(1)是干式工艺，生成薄膜均匀无针孔。
(2)等离子体聚合膜的耐溶剂性、耐化学腐蚀性、耐热性、耐磨损性能等化学、物理性质稳定。
(3)等离子体聚合膜与基体黏接性良好。
(4)在凹凸极不规则的基材表面也可制成均一薄膜。
(5)涂层制备温度低，可在常温条件下进行，有效避免对温度敏感器件的损伤。
(6)等离子体工艺不仅可以制备厚度为微米级的涂层而且可以制备超薄的纳米级涂层。
(7)涂层的可设计性强，在等离子体条件下，绝大多数有机物单体可被活化为具有较高活性的自由基，并在电子产品表面形成涂层。对单体偶极矩、化学惰性、自由体积的筛选与设计是获得绝缘性好、在较薄情况下具有优异防护性能的涂层的重要策略。
(8)涂层结构可控性强，可随时改变单体的成分和比例，使得涂层具有多层、梯度、调制等特殊结构。
(9)可制备无机和有机复合结构涂层。
目前，对于单一结构或单一组分的涂层，性能相对单一，要提高其防护性能，必须增加厚度，而增加厚度又会导致散热、信号透过等性能下降。
发明内容
本发明为解决上述技术问题提供一种具有调制结构的高绝缘纳米防护涂层的制备方法。该制备过程中，筛选出具有低偶极矩和高化学惰性的有机物单体，通过多官能度单体调控涂层的自由体积和致密性，使得涂层同时具有高绝缘性和优异的防护性。同时，该制备过程中，交替进行低偶极矩有机物涂层和有机硅涂层制备或有机氟碳涂层制备，形成低偶极矩-有机硅/氟碳的调制多层致密结构，复合调制多层结构的设计，可在不损失热传导和信号透过性能的条件下，实现涂层防护性能的大幅提升。
由于等离子化学气相沉积方法不仅可适用于多种单体，且对形成的涂层的成分与结构的可控性强，因此，通过单体的设计及工艺参数的优化，对涂层成分和结构进行调控与构筑， 可设计具有调制结构的纳米防护涂层。利用层与层之间的界面，阻止腐蚀的纵向扩散；同时由于调制纳米层状结构的超晶格效应，层层之间位错的堆积，使得涂层更不容易被击穿，耐水下通电能力得到有效提高。这种调制结构涂层在相同厚度下比派瑞林等现有涂层具有更优异的防护性能和绝缘性能。可在较低厚度情况下实现防护和绝缘，从而解决目前采用派瑞林等涂层时存在的诸多问题，如涂层厚度太厚、生产效率低、散热差、信号阻隔等。
本发明所采用的技术方案如下：
一种具有调制结构的高绝缘纳米防护涂层的制备方法，其特征在于：包括以下步骤：
(1)前处理：
将基材置于纳米涂层制备设备的反应腔室内，对反应腔室连续抽真空，将反应腔室内的真空度抽到10～200毫托，并通入惰性气体He、Ar或He和Ar混合气体，开启运动机构，使基材在反应腔室内产生运动；
(2)高绝缘纳米涂层的制备：
进行以下步骤至少一次，在基材表面制备高绝缘调制结构的纳米涂层：
通入单体A蒸汽到反应腔室内，至真空度为30～300毫托，开启等离子体放电，进行化学气相沉积，停止通入单体A蒸汽，通入单体B或单体C蒸汽，继续等离子体放电，进行化学气相沉积，停止通入单体B或单体C蒸汽；
所述单体A蒸汽成分包括：
至少一种低偶极矩有机物单体和至少一种多官能度不饱和烃及烃类衍生物的混合物，所述单体A蒸汽中多官能度不饱和烃及烃类衍生物所占的质量分数为15～65％；
所述单体B蒸汽成分包括：
至少一种单官能度不饱和氟碳树脂和至少一种多官能度不饱和烃及烃类衍生物的混合物，所述单体B蒸汽中多官能度不饱和烃及烃类衍生物所占的质量分数为15～65％；
所述单体C蒸汽成分包括：
至少一种含双键、Si-Cl、Si-O-C、Si-N-Si、Si-O-Si结构或环状结构的有机硅单体和至少一种多官能度不饱和烃及烃类衍生物的混合物，所述单体C蒸汽中多官能度不饱和烃类衍生物所占的质量分数为15～65％；
所述通入单体A、单体B和单体C蒸汽为将单体通过加料泵进行雾化、挥发并由低压10～200毫托引入反应腔室，所述通入单体A、单体B和单体C的流量均为10～1000μL/min；
(3)后处理：
停止等离子体放电，持续抽真空，保持反应腔室真空度为10～200毫托，1～5min后通入 空气至一个大气压，停止基材的运动，然后取出基材即可；
或者，停止等离子体放电，向反应腔室内充入空气或惰性气体至压力2000-5000毫托，然后抽真空至10-200毫托，进行上述充气和抽真空步骤至少一次，通入空气至一个大气压，停止基材的运动，然后取出基材即可。
在低真空等离子体放电环境下，通过对能量的有效输出，控制单体分子结构中较活泼的化学键发生断裂，形成活性较高的自由基，自由基与电子产品表面活化基团通过化学键结合，聚合形成纳米薄膜，最终在基材表面形成高绝缘性防护涂层。
所述步骤(1)中基材在反应腔室内产生运动，基材运动形式为基材相对反应腔室进行直线往复运动或曲线运动，所述曲线运动包括圆周运动、椭圆周运动、行星运动、球面运动或其他不规则路线的曲线运动。
所述步骤(1)中基材为固体材料，所述固体材料为电子产品、电器部件、电子组装半成品，PCB板、金属板、聚四氟乙烯板材或者电子元器件，且所述基材表面制备有机硅纳米涂层后其任一界面可暴露于水环境，霉菌环境，酸、碱性溶剂环境，酸、碱性盐雾环境，酸性大气环境，有机溶剂浸泡环境，化妆品环境，汗液环境，冷热循环冲击环境或湿热交变环境中使用。
所述步骤(1)中反应腔室为旋转体形腔室或者立方体形腔室，其容积为50～1000L，反应腔室的温度控制在30～60℃，所述惰性气体通入流量为5～300sccm。
所述步骤(2)中：通入单体A蒸汽、通入单体B蒸汽或通入单体C蒸汽，等离子体放电，进行化学气相沉积，沉积过程中等离子体放电过程包括小功率连续放电、脉冲放电或周期交替放电。
所述沉积过程中等离子体放电过程为小功率连续放电，具体包括以下沉积过程至少一次：
沉积过程包括预处理阶段和镀膜阶段，预处理阶段等离子体放电功率为150～600W，持续放电时间60～450s，然后进入镀膜阶段，调整等离子体放电功率为10～150W，持续放电时间600～3600s。
所述沉积过程中等离子体放电过程为脉冲放电，具体包括以下沉积过程至少一次：
沉积过程包括预处理阶段和镀膜阶段，预处理阶段等离子体放电功率为150～600W，持续放电时间60～450s，然后进入镀膜阶段，镀膜阶段为脉冲放电，功率10～300W，时间600s～3600s，脉冲放电的频率为1～1000HZ，脉冲的占空比为1:1～1:500。
所述沉积过程中等离子体放电过程为周期交替放电，具体包括以下沉积过程至少一次：
沉积过程包括预处理阶段和镀膜阶段，预处理阶段等离子体放电功率为150～600W，持续放电时间60～450s，然后进入镀膜阶段，镀膜阶段等离子体为周期交替变化放电输出，功率10～300W，时间600s～3600s，交变频率为1-1000Hz，等离子体周期交替变化放电输出波形为锯齿波形、正弦波形、方波波形、全波整流波形或半波整流波形。
所述低偶极矩有机物单体包括：
对二甲苯、苯、甲苯、四氟化碳、α-甲基苯乙烯、聚对二氯甲苯、二甲基硅氧烷、分子量500-50000的聚二甲基硅氧烷、烯丙苯、十氟联苯、十氟联苯酮、全氟烯丙基苯、四氟乙烯、六氟丙烯、1H,1H-全氟辛基胺、全氟碘代十二烷、全氟三丁胺、1,8-二碘代全氟辛烷、全氟己基碘烷、全氟碘代丁烷、全氟碘代癸烷、全氟辛基碘烷、1,4-二(2',3'-环氧丙基)全氟丁烷、十二氟-2-甲基-2-戊烯、2-(全氟丁基)乙基甲基丙烯酸酯、2-(全氟辛基)乙基甲基丙烯酸酯、2-(全氟辛基)碘代乙烷、全氟癸基乙基碘、1,1,2,2-四氢全氟己基碘、全氟丁基乙烯、1H,1H,2H-全氟-1-癸烯、2,4,6-三(全氟庚基)-1,3,5-三嗪、全氟己基乙烯、3-(全氟正辛基)-1,2-环氧丙烷、全氟环醚、全氟十二烷基乙烯、全氟十二烷基乙基碘、二溴对二甲苯、1,1,4,4-四苯基-1,3-丁二烯；
所述单官能度不饱和氟碳树脂包括：
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、(全氟环己基)甲基丙烯酸酯、3,3,3-三氟-1-丙炔、1-乙炔基-3,5-二氟苯或4-乙炔基三氟甲苯；
所述含双键、Si-Cl、Si-O-C、Si-N-Si、Si-O-Si结构或环状结构的有机硅单体包括：
含双键结构的有机硅单体：烯丙基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三甲基硅烷、3-丁烯基三甲基硅烷、乙烯基三丁酮肟基硅烷、四甲基二乙烯基二硅氧烷、1,2,2-三氟乙烯基三苯基硅烷；
含Si-Cl键的有机硅单体：三苯基氯硅烷、甲基乙烯基二氯硅烷、三氟丙基三氯硅烷、三氟丙基甲基二氯硅烷、二甲基苯基氯硅烷、三丁基氯硅烷、苄基二甲基氯硅烷；
含Si-O-C结构的有机硅单体：四甲氧基硅烷、三甲氧基氢硅氧烷、正辛基三乙氧基硅烷、苯基三乙氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷、三乙基乙烯基硅烷、六乙基环三硅氧烷、3-(甲基丙烯酰氧)丙基三甲氧基硅烷、苯基三(三甲基硅氧烷基)硅烷、二苯基二乙氧基硅烷、十二烷基三甲氧基硅烷、正辛基三乙氧基硅烷、二甲氧基硅烷、3-氯丙基三甲氧基硅烷；
含Si-N-Si或Si-O-Si结构的有机硅单体：六甲基二硅烷基胺、六甲基环三硅烷氨基、六甲基二硅氮烷、六甲基二硅醚；
含环状结构的有机硅单体：六甲基环三硅氧烷、八甲基环四硅氧烷、六苯基环三硅氧烷、十甲基环五硅氧烷、八苯基环四硅氧烷、三苯基羟基硅烷、二苯基二羟基硅烷、铬酸双(三苯甲基硅烷基)酯、三氟丙基甲基环三硅氧烷、2,2,4,4-四甲基-6,6,8,8-四苯基环四硅氧烷、四甲基四乙烯基环四硅氧烷、3-缩水甘油醚氧基丙基三乙氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷；
所述多官能度不饱和烃及烃类衍生物包括：
1,3-丁二烯、异戊二烯、1,4-戊二烯、乙氧基化三羟甲基丙烷三丙烯酸酯、二缩三丙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、二丙烯酸乙二醇酯、二乙二醇二乙烯基醚或二丙烯酸新戊二醇酯。
所述步骤(2)中，所述等离子体放电方式为射频放电、微波放电、中频放电、高频放电、电火花放电，所述高频放电和中频放电的波形为正弦或双极脉冲，射频等离子体是利用高频电磁场放电而产生的等离子体。微波法是利用微波的能量激发等离子体，具有能量利用效率高的优点，同时由于无电极放电，等离子体纯净，是目前高质量、高速率、大面积制备的优异方法。
涂层制备过程中，基材的运动特性和等离子体放电能量组合联动。制备过程中等离子体放电的同时，基材产生运动，提高了涂层沉积效率，并改善了涂层厚度的均匀性和致密性。
所制备的涂层具有绝缘、防水防潮，防霉菌，耐酸、碱性溶剂，耐酸、碱性盐雾，耐酸性大气，耐有机溶剂浸泡，耐化妆品，耐汗液，耐冷热循环冲击(-40℃～+75℃)，耐湿热交变(湿度75％～95％)等特性。具备上述防护性能的同时，涂层厚度在1～1000nm情况下，对频率在10M～8G范围内的射频通讯信号的影响低于5％。
本发明的上述技术方案与现有技术相比具有以下优点：
1、等离子体化学气相沉积技术方法，比液相法三防涂层涂敷方法更环保；而相比蒸镀派瑞林方法，沉积温度低、速度更快、涂层结构和成分的可控性强，单体的可选择性强。
2、基材在反应腔室内发生运动，使不同位置的基材镀膜厚度趋向一致，解决了由于反应腔室内不同区域单体密度不同导致基材表面涂层厚度不均匀的问题。制备过程中，基材的运动特性和等离子体放电能量组合联动，放电能量输出的同时，基材进行运动，提高了沉积效率，使得到的防护涂层致密性显著提高。同时由于沉积效率的提高，单体蒸汽的化学单体原材料的用量也仅有其他现有技术中用量的10％～15％，从而减少了尾气废气的排放，更加绿色环保，在提高实际生产效能中具有重大的意义。
3、本发明筛选出具有低偶极矩和高化学惰性的有机物单体，通过多官能度单体调控涂层的自由体积和致密性，使得涂层同时具有高绝缘性和优异的防护性。
(1)本发明选择具有高对称性苯环及其苯衍生物或全氟化合物作为单体，其聚合后分子由于对称或者各碳原子被大量氟原子包覆，极性较低，其介电常数非常低，小于2.7，绝缘性高；
(2)由于苯环结构和氟碳结构具有较高的化学惰性，其形成的聚合物具有优异的化学稳定性；
(3)通过交联剂分子链的长短和官能度，可有效提高涂层的致密性和自由体积，从而提高绝缘性和防护性。
(4)通过引入交联结构的其他单体，控制单体配比，根据不同单体的分子键能、键长的差异、汽化温度的差异，给予设备相应的能量输出及工艺参数的有效变化，获得调制、复合、渐变结构的聚合物纳米涂层，如--高绝缘层--氟碳层--高绝缘层--氟碳层—结构涂层，既保证 了薄膜的绝缘性，又提高了电子产品等产品的耐环境腐蚀的性能。
4、本发明采用交替进行低偶极矩有机物涂层和有机硅涂层制备或有机氟碳涂层制备的方式，形成低偶极矩-有机硅/氟碳的调制多层致密结构，可降低涂层的应力，提高涂层的韧性；同时由于低偶极矩-有机硅/氟碳之间存在横向界面，腐蚀介质对涂层进行腐蚀过程中，遇到横向界面，则腐蚀会往横向发展，而不容易形成贯穿涂层的纵向腐蚀，避免腐蚀介质透过涂层而腐蚀被保护的材料与器件；同时，由于调制纳米层状结构的超晶格效应，层层之间位错的堆积，使得涂层更不容易被击穿，耐水下通电能力得到有效提高。
5、本发明采用等离子体化学气相沉积，通过对单体和涂层结构调控，获得具有调制结构的纳米防护涂层。这种涂层具有以下优点：每个周期由一层纳米级低偶极矩和纳米级有机硅涂层或有机氟碳涂层组成，涂层总厚度控制在20nm-10μm之间可控；硬度在HB-4H之间可控；同时具有优异的绝缘性能、耐水下通电性能和较低的表面能；具有优异的三防性能。
6、本发明方法较一般的单次长时间镀膜，获得的涂层其结合力和致密度至少分别提高了40％-50％和35％-50％，耐水下通电能力提高40％-50％。该循环周期交替放得到的调制结构涂层性能优异，实用性较强。
7、一般等离子体聚合选用单官能度碳氢氧有机化合物单体，得到具有一定交联结构涂层。交联结构是由于单体在等离子体放电时发生断链形成的众多活性点通过交互连接的方式而形成交联结构。但是这种交联结构较为疏松，含有较多的线性成分，耐溶液渗透和溶解性差。相比于传统单官能度有机物单体，在等离子体条件下，有机硅单体中的与硅连接的官能团相互之间能够发生缩合反应，因此，单体和单体之间可发生立体网状交联，可进一步提高涂层的致密性、耐磨性及抗腐蚀性。相同厚度的有机硅涂层硬度比传统涂层硬度高1-2个等级，耐盐雾能力提高30-50％。
日常生活中的电子设备极易受腐蚀环境的侵蚀而损坏，在使用的过程中基本处于腐蚀环境中，长此以往，会造成电子设备短路和断路等损害。本发明专利的镀膜方法大大增加了纳米在提高实际生产效能中具有重大的意义。提高了涂层在腐蚀性环境的使用寿命，提高了产品的保护效果。主要应用于以下产品：
(1)、便携设备键盘：便携式键盘具有小而轻的特点，常用于计算机，手机等设备。其能便于用户在旅程中办公。但是当其遇到常见液体的污染，如盛水茶杯的意外翻倒，雨水、汗液的浸透，键盘内部容易短路，进而损坏。使用该类纳米涂层对其进行镀膜后，当能够保障键盘表面易清理，遇水后功能完好，使得键盘能够适应更加严峻的环境。
(2)、LED显示屏：LED显示屏有商品宣传，店面装饰，照明，警示等用途。其部分用 途需要面对雨水或者多粉尘的恶劣环境，如下雨天时，商场露天LED广告屏幕，路面警示灯，生产车间的LED显示屏控制面板，这些恶劣环境导致LED屏幕失灵，而且容易积灰，不易清洗，使用该纳米涂层后，能够有效解决上述问题。
(3)、智能指纹锁：指纹锁是智能锁具，它集合了计算机信息技术、电子技术、机械技术和现代五金工艺，被广泛应用于公安刑侦及司法领域。但是其遇水后，其内部线路易短路，难以修复，需要暴力拆锁，使用该涂层后，能够避免这一问题。
(4)、助听器、蓝牙耳机：助听器与蓝牙耳机均没有通讯线，使用该涂层后，用户可以在一定时间内在有水环境下使用，如洗澡，下雨天，设备均不会因为雨水浸润被损坏。
(5)、部分传感器：部分传感器需要在液体环境中工作，如水压、油压传感器，以及水下作业设备中用到的传感器，以及工作环境经常遇水的传感器，这些传感器在使用该涂层后，能够保障不会因为液体入侵机械设备内部结构而导致传感器失灵。
(6)、大多数3C产品：如移动电话、笔记本、PSP等。
(7)、其他需要防水的设备：包括需要在潮湿环境中作业，或者可能遇到常见液体泼洒等意外情况，会影响内部弱电线路正常运行的设备。
该方法制备的有机硅纳米涂层还可以适用于以下不同的环境及其涉及的相关产品：
防水防潮防霉菌：
1房屋内饰：卫生间顶面、墙纸、吊灯、窗帘、窗纱。2生活用品：蚊帐，台灯罩、筷子篓、汽车后视镜。3文物及艺术品：字帖、古玩、木雕、皮革、青铜器、丝绸、古装、古籍。4电子元器件及电子产品：传感器(潮湿或者多尘环境中作业)、各类电子产品(电子血压计、智能手表)的芯片、线路板、手机、LED屏幕、助听器。5精密仪器及光学设备：机械手表、显微镜。
耐酸、碱性溶剂，耐酸、碱性盐雾，耐酸性大气：
1住房内饰件：墙纸、瓷砖。2防护用具：耐酸(碱)手套、耐酸(碱)防护服。3机械设备及管道：烟道脱硫设备、密封件(酸/碱性润滑油)、管道、阀门、大管径海用输送管道内衬等处。4各种反应釜、反应器。5化学药品生产、储存；污水处理、曝气池；6其它：酸碱车间、防碱航空航天、能源电力、钢铁冶金、石油化工、医疗等各行业、贮藏容器、雕像(减小酸雨对其的腐蚀)、传感器(酸/碱性性环境下)。
耐有机溶剂浸泡，耐化妆品，耐汗液：
1如链烷烃、烯烃、醇、醛、胺、酯、醚、酮、芳香烃、氢化烃、萜烯烃、卤代烃、杂环化物、含氮化合物及含硫化合物溶剂等；2化妆品包装容器；3指纹锁、耳机。
耐冷热循环冲击(-40℃～+75℃)，耐湿热交变(湿度75％～95％)：电工、电子、汽车电器，如航空、汽车、家电、科研等领域的设备。
具体实施方式
下面结合具体实施例详细说明本发明，但本发明并不局限于具体实施例。
实施例1
一种具有调制结构的高绝缘纳米防护涂层的制备方法，包括以下步骤：
(1)前处理：
将基材置于纳米涂层制备设备的反应腔室内，闭合反应腔室并对反应腔室连续抽真空，将反应腔室内的真空度抽到10毫托，通入惰性气体Ar，开启运动机构，使基材在反应腔室内产生运动；
步骤(1)中基材为固体材料，所述固体材料为块状铝制材料和PCB板，且所述基材表面制备耐冷热循环冲击涂层后其任一界面可暴露于冷、热循环测试环境中。
步骤(1)中反应腔室为旋转体形腔室，反应腔室的容积为50L，反应腔室的温度控制在30℃，通入惰性气体的流量为5sccm。
步骤(1)中基材在反应腔室内产生运动，基材运动形式为基材相对反应腔室进行圆周运动，转速为10转/min。
(2)高绝缘纳米涂层的制备：
进行以下步骤12次，在基材表面制备高绝缘调制结构的纳米涂层：
通入单体A蒸汽到反应腔室内，至真空度为40毫托，开启等离子体放电，进行化学气相沉积，停止通入单体A蒸汽，通入单体B蒸汽，继续等离子体放电，进行化学气相沉积，停止通入单体B蒸汽；
所述单体A蒸汽成分包括：
一种低偶极矩有机物单体和两种多官能度不饱和烃及烃类衍生物的混合物，所述单体A蒸汽中多官能度不饱和烃及烃类衍生物所占的质量分数为15％，
所述一种低偶极矩有机物单体为：1,8-二碘代全氟辛烷，
所述两种多官能度不饱和烃及烃类衍生物为：1,3-丁二烯、乙氧基化三羟甲基丙烷三丙烯酸酯；
所述单体B蒸汽成分包括：
一种单官能度不饱和氟碳树脂和三种多官能度不饱和烃及烃类衍生物的混合物，所述单体B蒸汽中多官能度不饱和烃及烃类衍生物所占的质量分数为65％，
所述一种单官能度不饱和氟碳树脂为：2-(全氟十二烷基)乙基丙烯酸酯
所述三种多官能度不饱和烃及烃类衍生物为：1,4-戊二烯、二缩三丙二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯；
所述通入单体A、单体B蒸汽为将单体通过加料泵进行雾化、挥发并由低压10毫托引入反应腔室，所述通入单体A、单体B的流量均为10μL/min；
所述步骤(2)中通入单体A蒸汽或通入单体B蒸汽，等离子体放电，进行化学气相沉积，沉积过程中等离子体放电过程均为小功率连续放电，具体包括以下沉积过程一次：
沉积过程包括预处理阶段和镀膜阶段，预处理阶段等离子体放电功率为150W，持续放电时间450s，然后进入镀膜阶段，调整等离子体放电功率为10W，持续放电时间3600s。
所述步骤(2)中，等离子体放电方式为射频放电；
(3)后处理：
停止等离子体放电，持续抽真空，保持反应腔室真空度为10毫托，1min后通入空气至一个大气压，然后取出基材即可。
上述过程得到的涂层介电常数为2.73，镀膜后的铝制材料和PCB板，冷、热循环冲击测试效果如下：
Figure PCTCN2018082837-appb-000001
上述镀膜后的铝制材料，湿热交变测试效果如下：
Figure PCTCN2018082837-appb-000002
实施例2
一种具有调制结构的高绝缘纳米防护涂层的制备方法，包括以下步骤：
(1)将基材置于纳米涂层制备设备反应腔室内，闭合反应腔室并对反应腔室连续抽真空，将反应腔室内的真空度抽到30毫托，通入惰性气体He，启动运动机构，使基材进行运动；
步骤(1)中基材为固体材料，所述固体材料为块状铝制材料，且所述基材表面制备耐湿热交变涂层后其任一界面可暴露于湿热测试环境中。
步骤(1)中反应腔室为立方体形腔室，反应腔室的容积为270L，反应腔室的温度控制在42℃，通入惰性气体的流量为18sccm。
步骤(1)中基材进行行星运动，公转速度为4转/min，自转速度为10转/min。
(2)高绝缘纳米涂层的制备：
进行以下步骤1次，在基材表面制备高绝缘调制结构的纳米涂层：
通入单体A蒸汽到反应腔室内，至真空度为70毫托，开启等离子体放电，进行化学气相沉积，停止通入单体A蒸汽，通入单体C蒸汽，继续等离子体放电，进行化学气相沉积，停止通入单体C蒸汽；
所述单体A蒸汽成分包括：
三种低偶极矩有机物单体和一种多官能度不饱和烃及烃类衍生物的混合物，所述单体A蒸汽中多官能度不饱和烃及烃类衍生物所占的质量分数为29％，
所述三种低偶极矩有机物单体为：分子量50000的聚二甲基硅氧烷、十氟联苯酮、六氟丙烯；
所述一种多官能度不饱和烃及烃类衍生物为：二丙烯酸乙二醇酯；
所述单体C蒸汽成分包括：
一种含双键结构的有机硅单体和四种多官能度不饱和烃及烃类衍生物的混合物，所述单体C蒸汽中多官能度不饱和烃及烃类衍生物所占的质量分数为32％；
所述一种含双键结构的有机硅单体为：乙烯基三丁酮肟基硅烷，
所述四种多官能度不饱和烃及烃类衍生物为：异戊二烯、1,4-戊二烯、二缩三丙二醇二丙烯酸酯、二乙二醇二乙烯基醚；
所述通入单体A、单体C蒸汽为将单体通过加料泵进行雾化、挥发并由低压30毫托引入反应腔室，所述通入单体A、单体C的流量均为85μL/min；
所述步骤(2)中通入单体A蒸汽或通入单体C蒸汽，等离子体放电，进行化学气相沉积，沉积过程中等离子体放电过程均为小功率连续放电，具体包括以下沉积过程5次：
沉积过程包括预处理阶段和镀膜阶段，预处理阶段等离子体放电功率为600W，持续放 电时间60s，然后进入镀膜阶段，调整等离子体放电功率为150W，持续放电时间600s。
所述步骤(2)中，等离子体放电方式为微波放电；
(3)后处理：
停止等离子体放电，持续抽真空，保持反应腔室真空度为60毫托，2min后通入空气至一个大气压，然后取出基材即可。
上述过程获得的涂层介电常数为2.45，铝制材料镀膜后，冷热循环冲击测试效果如下：
Figure PCTCN2018082837-appb-000003
上述镀膜后的铝制材料，湿热交变测试效果如下：
Figure PCTCN2018082837-appb-000004
实施例3
一种具有调制结构的高绝缘纳米防护涂层的制备方法，包括以下步骤：
(1)将基材置于纳米涂层制备设备反应腔室内，闭合反应腔室并对反应腔室连续抽真空，将反应腔室内的真空度抽到80毫托，通入惰性气体Ar和He的混合气体，启动运动机构，使基材进行运动；
步骤(1)中基材为固体材料，所述固体材料为块状聚四氟乙烯板和电器部件，且所述块状聚四氟乙烯板表面制备防霉菌涂层后其任一界面可暴露于GJB150.10A-2009霉菌测试环境中使用，所述电器部件表面制备防水耐电击穿涂层后其任一界面可暴露于国际工业防水等级标准IPX7所述的环境使用。
步骤(1)中反应腔室为旋转体形腔室，反应腔室的容积为580L，反应腔室的温度控制在53℃，通入惰性气体的流量为65sccm。
步骤(1)中基材进行圆周运动，转速为12转/min。
(2)高绝缘纳米涂层的制备：
进行以下步骤8次，在基材表面制备高绝缘调制结构的纳米涂层：
通入单体A蒸汽到反应腔室内，至真空度为120毫托，开启等离子体放电，进行化学气相沉积，停止通入单体A蒸汽，通入单体C蒸汽，继续等离子体放电，进行化学气相沉积，停止通入单体C蒸汽；
所述单体A蒸汽成分包括：
四种低偶极矩有机物单体和两种多官能度不饱和烃及烃类衍生物的混合物，所述单体A蒸汽中多官能度不饱和烃及烃类衍生物所占的质量分数为48％，
所述四种低偶极矩有机物单体为：甲苯、α-甲基苯乙烯、二甲基硅氧烷、十氟联苯酮，
所述两种多官能度不饱和烃及烃类衍生物为：异戊二烯、二丙烯酸新戊二醇酯；
所述单体C蒸汽成分包括：
五种含Si-Cl结构的有机硅单体和两种多官能度不饱和烃及烃类衍生物的混合物，所述单体C蒸汽中多官能度不饱和烃及烃类衍生物所占的质量分数为52％；
所述五种含Si-Cl结构的有机硅单体为：三苯基氯硅烷、三氟丙基甲基二氯硅烷、二甲基苯基氯硅烷、三丁基氯硅烷、苄基二甲基氯硅烷，
所述两种多官能度不饱和烃及烃类衍生物为：聚乙二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯；
所述通入单体A、单体C蒸汽为将单体通过加料泵进行雾化、挥发并由低压80毫托引入反应腔室，所述通入单体A、单体C的流量均为440μL/min；
所述步骤(2)中通入单体A蒸汽或通入单体C蒸汽，等离子体放电，进行化学气相沉积，所述沉积过程中等离子体放电过程为脉冲放电，具体包括以下沉积过程一次：
沉积过程包括预处理阶段和镀膜阶段，预处理阶段等离子体放电功率为150W，持续放电时间450s，然后进入镀膜阶段，镀膜阶段为脉冲放电，功率10W，时间3600s，脉冲放电的频率为1HZ，脉冲的占空比为1:500；
所述步骤(2)中，等离子体放电方式为电火花放电；
(3)后处理：
停止等离子体放电，持续抽真空，保持反应腔室真空度为100毫托，3min后通入空气至一个大气压，然后取出基材即可。
上述过程获得的涂层介电常数为2.46，聚四氟乙烯板镀膜后，GJB150.10A-2009霉菌测试结果：
Figure PCTCN2018082837-appb-000005
Figure PCTCN2018082837-appb-000006
制备防水耐电击穿涂层电器部件在不同电压下测试水下浸泡实验结果：
Figure PCTCN2018082837-appb-000007
IPX 7防水等级测试(水下1m浸水试验30min)结果：
Figure PCTCN2018082837-appb-000008
实施例4
一种具有调制结构的高绝缘纳米防护涂层的制备方法，包括以下步骤：
(1)将基材置于纳米涂层制备设备反应腔室内，闭合反应腔室并对反应腔室连续抽真空，将反应腔室内的真空度抽到100毫托，通入惰性气体Ar，启动运动机构，使基材进行运动；
步骤(1)中基材为固体材料，所述固体材料为块状聚四氟乙烯板和电器部件，且所述块状聚四氟乙烯板表面制备防霉菌涂层后其任一界面可暴露于GJB150.10A-2009霉菌测试环境中使用，所述电器部件表面制备防水耐电击穿涂层后其任一界面可暴露于国际工业防水等级标准IPX7所述的环境使用。
步骤(1)中反应腔室的容积为640L，反应腔室的温度控制在54℃，通入惰性气体的流量为240sccm。
步骤(1)中基材进行直线往复运动，运动速度为23mm/min。
(2)高绝缘纳米涂层的制备：
进行以下步骤15次，在基材表面制备高绝缘调制结构的纳米涂层：
通入单体A蒸汽到反应腔室内，至真空度为150毫托，开启等离子体放电，进行化学气相沉积，停止通入单体A蒸汽，通入单体B蒸汽，继续等离子体放电，进行化学气相沉积，停止通入单体B蒸汽；
所述单体A蒸汽成分包括：
五种低偶极矩有机物单体和三种多官能度不饱和烃及烃类衍生物的混合物，所述单体A 蒸汽中多官能度不饱和烃及烃类衍生物所占的质量分数为65％，
所述五种低偶极矩有机物单体为：对二甲苯、1H,1H-全氟辛基胺、2-(全氟辛基)乙基甲基丙烯酸酯、1,1,2,2-四氢全氟己基碘、2,4,6-三(全氟庚基)-1,3,5-三嗪，
所述三种多官能度不饱和烃及烃类衍生物为：异戊二烯、二缩三丙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯；
所述单体B蒸汽成分包括：
四种单官能度不饱和氟碳树脂和四种多官能度不饱和烃及烃类衍生物的混合物，所述单体B蒸汽中多官能度不饱和烃及烃类衍生物所占的质量分数为15％，
所述四种单官能度不饱和氟碳树脂为：2-(全氟丁基)乙基丙烯酸酯、(全氟环己基)甲基丙烯酸酯、3,3,3-三氟-1-丙炔、4-乙炔基三氟甲苯，
所述四种多官能度不饱和烃及烃类衍生物为：异戊二烯、1,4-戊二烯、聚乙二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯；
所述通入单体A、单体B蒸汽为将单体通过加料泵进行雾化、挥发并由低压100毫托引入反应腔室，所述通入单体A、单体B的流量均为1000μL/min；
所述步骤(2)中通入单体A蒸汽或通入单体B蒸汽，等离子体放电，进行化学气相沉积，所述沉积过程中等离子体放电过程为脉冲放电，具体包括以下沉积过程七次：
沉积过程包括预处理阶段和镀膜阶段，预处理阶段等离子体放电功率为600W，持续放电时间60s，然后进入镀膜阶段，镀膜阶段为脉冲放电，功率300W，时间600s，脉冲放电的频率为1000HZ，脉冲的占空比为1:1；
所述步骤(2)中，等离子体放电方式为高频放电，高频放电的波形为正弦；
(3)后处理：
停止通入单体蒸汽，同时停止等离子体放电，持续抽真空，保持反应腔室真空度为200毫托，4min后通入空气至一个大气压，然后取出基材即可。
上述过程得到的涂层介电常数为2.48，聚四氟乙烯板镀膜后，GJB150.10A-2009霉菌测试结果：
Figure PCTCN2018082837-appb-000009
制备防水耐电击穿涂层电器部件在不同电压下测试水下浸泡实验结果：
Figure PCTCN2018082837-appb-000010
IPX 7防水等级测试(水下1m浸水试验30min)结果：
Figure PCTCN2018082837-appb-000011
实施例5
一种具有调制结构的高绝缘纳米防护涂层的制备方法，包括以下步骤：
(1)将基材置于纳米涂层制备设备反应腔室内，闭合反应腔室并对反应腔室连续抽真空，将反应腔室内的真空度抽到200毫托，通入惰性气体Ar和He的混合气体，启动运动机构，使基材进行运动；
步骤(1)中基材为固体材料，所述固体材料为块状铝制材料，且所述基材表面制备耐酸、碱性环境涂层后其任一界面可暴露于酸、碱测试环境中。
步骤(1)中反应腔室的容积为1000L，反应腔室的温度控制在60℃，通入惰性气体的流量为300sccm。
步骤(1)中基材进行曲线往复运动，速度为50mm/min。
(2)高绝缘纳米涂层的制备：
进行以下步骤26次，在基材表面制备高绝缘调制结构的纳米涂层：
通入单体A蒸汽到反应腔室内，至真空度为300毫托，开启等离子体放电，进行化学气相沉积，停止通入单体A蒸汽，通入单体C蒸汽，继续等离子体放电，进行化学气相沉积，停止通入单体C蒸汽；
所述单体A蒸汽成分包括：
六种低偶极矩有机物单体和三种多官能度不饱和烃及烃类衍生物的混合物，所述单体A蒸汽中多官能度不饱和烃及烃类衍生物所占的质量分数为56％，
所述六种低偶极矩有机物单体为：苯、α-甲基苯乙烯、二甲基硅氧烷、烯丙苯、2-(全氟丁基)乙基甲基丙烯酸酯、1,1,2,2-四氢全氟己基碘，
所述三种多官能度不饱和烃及烃类衍生物为：1,4-戊二烯、聚乙二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯；
所述单体C蒸汽成分包括：
四种含Si-O-C结构的有机硅单体和三种多官能度不饱和烃及烃类衍生物的混合物，所述单体C蒸汽中多官能度不饱和烃及烃类衍生物所占的质量分数为65％；
所述四种含Si-O-C结构的有机硅单体为：三甲氧基氢硅氧烷、正辛基三乙氧基硅烷、三乙基乙烯基硅烷、3-(甲基丙烯酰氧)丙基三甲氧基硅烷，
所述三种多官能度不饱和烃及烃类衍生物为：1,4-戊二烯、乙氧基化三羟甲基丙烷三丙烯酸酯、聚乙二醇二丙烯酸酯；
所述通入单体A、单体C蒸汽为将单体通过加料泵进行雾化、挥发并由低压200毫托引入反应腔室，所述通入单体A、单体C的流量均为780μL/min；
所述步骤(2)中通入单体A蒸汽或通入单体C蒸汽，等离子体放电，进行化学气相沉积，所述沉积过程中等离子体放电过程为周期交替放电，具体包括以下沉积过程一次：
沉积过程包括预处理阶段和镀膜阶段，预处理阶段等离子体放电功率为150W，持续放电时间450s，然后进入镀膜阶段，镀膜阶段等离子体为周期交替变化放电输出，功率10W，时间3600s，交变频率为1Hz，等离子体周期交替变化放电输出波形为锯齿波形。
所述步骤(2)中，等离子体放电方式为中频放电，中频放电的波形为双极脉冲；
(3)后处理：
停止等离子体放电，向反应腔室内充入空气至压力2000毫托，然后抽真空至10毫托，进行上述充气和抽真空步骤十次，通入空气至一个大气压，停止基材的运动，然后取出基材即可上述过程所获涂层及镀膜后的铝制材料，测试效果如下：
Figure PCTCN2018082837-appb-000012
(2)耐有机溶剂测试结果：(pass表示浸泡一段时间后接触角变化小于5°)
Figure PCTCN2018082837-appb-000013
(3)酸、碱性测试结果：(pass表示实验一段时间后不发生腐蚀现象)
Figure PCTCN2018082837-appb-000014
Figure PCTCN2018082837-appb-000015
实施例6
一种具有调制结构的高绝缘纳米防护涂层的制备方法，包括以下步骤：
(1)将基材置于纳米涂层制备设备反应腔室内，闭合反应腔室并对反应腔室连续抽真空，将反应腔室内的真空度抽到160毫托，通入惰性气体Ar，启动运动机构，使基材进行运动；
步骤(1)基材为固体材料，所述固体材料为块状铝制材料和电器部件，且所述基材表面制备高绝缘性涂层后其任一界面可暴露于有机溶剂测试环境中。
步骤(1)中反应腔室的容积为400L，反应腔室的温度控制在40℃，通入惰性气体的流量为150sccm。
步骤(1)中基材进行曲线往复运动，速度为30mm/min。
(2)高绝缘纳米涂层的制备：
进行以下步骤35次，在基材表面制备高绝缘调制结构的纳米涂层：
通入单体A蒸汽到反应腔室内，至真空度为230毫托，开启等离子体放电，进行化学气相沉积，停止通入单体A蒸汽，通入单体C蒸汽，继续等离子体放电，进行化学气相沉积，停止通入单体C蒸汽；
所述单体A蒸汽成分包括：
五种低偶极矩有机物单体和四种多官能度不饱和烃及烃类衍生物的混合物，所述单体A蒸汽中多官能度不饱和烃及烃类衍生物所占的质量分数为65％，
所述五种低偶极矩有机物单体为：烯丙苯、十氟联苯酮、六氟丙烯、1H,1H-全氟辛基胺、全氟辛基碘烷，
所述四种多官能度不饱和烃及烃类衍生物为：1,4-戊二烯、乙氧基化三羟甲基丙烷三丙烯酸酯、聚乙二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯；
所述单体C蒸汽成分包括：
六种含环状结构的有机硅单体和四种多官能度不饱和烃及烃类衍生物的混合物，所述单 体C蒸汽中多官能度不饱和烃及烃类衍生物所占的质量分数为40％；
所述六种含环状结构的有机硅单体：六苯基环三硅氧烷、八苯基环四硅氧烷、二苯基二羟基硅烷、铬酸双(三苯甲基硅烷基)酯、三氟丙基甲基环三硅氧烷、2,2,4,4-四甲基-6,6,8,8-四苯基环四硅氧烷，
所述四种多官能度不饱和烃及烃类衍生物为：1,3-丁二烯、异戊二烯、乙氧基化三羟甲基丙烷三丙烯酸酯、二丙烯酸乙二醇酯；
所述通入单体A、单体C蒸汽为将单体通过加料泵进行雾化、挥发并由低压160毫托引入反应腔室，所述通入单体A、单体C的流量均为460μL/min；
所述步骤(2)中通入单体A蒸汽或通入单体C蒸汽，等离子体放电，进行化学气相沉积，所述沉积过程中等离子体放电过程为周期交替放电，具体包括以下沉积过程五次：
沉积过程包括预处理阶段和镀膜阶段，预处理阶段等离子体放电功率为600W，持续放电时间60s，然后进入镀膜阶段，镀膜阶段等离子体为周期交替变化放电输出，功率300W，时间600s，交变频率为1000Hz，等离子体周期交替变化放电输出波形为半波整流波形。
所述步骤(2)中，等离子体放电方式为微波放电
(3)后处理：
停止等离子体放电，向反应腔室内充入惰性气体至压力5000毫托，然后抽真空至200毫托，进行上述充气和抽真空步骤一次，通入空气至一个大气压，停止基材的运动，然后取出基材即可
上述镀膜后的铝制材料，测试效果如下：
(1)疏水疏油性
Figure PCTCN2018082837-appb-000016
(2)上述镀膜后的电器部件在不同电压下测试水下浸泡实验结果：
Figure PCTCN2018082837-appb-000017
(3)耐有机溶剂测试结果：(pass表示浸泡一段时间后接触角变化小于5°)
Figure PCTCN2018082837-appb-000018
Figure PCTCN2018082837-appb-000019
(4)酸、碱性测试结果：(pass表示实验一段时间后不发生腐蚀现象)
Figure PCTCN2018082837-appb-000020

Claims (10)

  1. 一种具有调制结构的高绝缘纳米防护涂层的制备方法，其特征在于：包括以下步骤：
    (1)前处理：
    将基材置于纳米涂层制备设备的反应腔室内，对反应腔室连续抽真空，将反应腔室内的真空度抽到10～200毫托，并通入惰性气体He、Ar或He和Ar混合气体，开启运动机构，使基材在反应腔室内产生运动；
    (2)高绝缘纳米涂层的制备：
    进行以下步骤至少一次，在基材表面制备高绝缘调制结构的纳米涂层：
    通入单体A蒸汽到反应腔室内，至真空度为30～300毫托，开启等离子体放电，进行化学气相沉积，停止通入单体A蒸汽，通入单体B或单体C蒸汽，继续等离子体放电，进行化学气相沉积，停止通入单体B或单体C蒸汽；
    所述单体A蒸汽成分包括：
    至少一种低偶极矩有机物单体和至少一种多官能度不饱和烃及烃类衍生物的混合物，所述单体A蒸汽中多官能度不饱和烃及烃类衍生物所占的质量分数为15～65％；
    所述单体B蒸汽成分包括：
    至少一种单官能度不饱和氟碳树脂和至少一种多官能度不饱和烃及烃类衍生物的混合物，所述单体B蒸汽中多官能度不饱和烃及烃类衍生物所占的质量分数为15～65％；
    所述单体C蒸汽成分包括：
    至少一种含双键、Si-Cl、Si-O-C、Si-N-Si、Si-O-Si结构或环状结构的有机硅单体和至少一种多官能度不饱和烃及烃类衍生物的混合物，所述单体C蒸汽中多官能度不饱和烃类衍生物所占的质量分数为15～65％；
    所述通入单体A、单体B和单体C的流量均为10～1000μL/min；
    (3)后处理：
    停止等离子体放电，持续抽真空，保持反应腔室真空度为10～200毫托，1～5min后通入空气至一个大气压，停止基材的运动，然后取出基材即可；
    或者，停止等离子体放电，向反应腔室内充入空气或惰性气体至压力2000-5000毫托，然后抽真空至10-200毫托，进行上述充气和抽真空步骤至少一次，通入空气至一个大气压，停止基材的运动，然后取出基材即可。
  2. 根据权利要求1所述的一种具有调制结构的高绝缘纳米防护涂层的制备方法，其特征在于：所述步骤(1)中基材在反应腔室内产生运动，基材运动形式为基材相对反应腔室进行直线往复运动或曲线运动，所述曲线运动包括圆周运动、椭圆周运动、行星运动、球面运动或其他不规则路线的曲线运动。
  3. 根据权利要求1所述的一种具有调制结构的高绝缘纳米防护涂层的制备方法，其特征在于：所述步骤(1)中基材为固体材料，所述固体材料为电子产品、电器部件、电子组装半成品，PCB板、金属板、聚四氟乙烯板材或者电子元器件，且所述基材表面制备有机硅纳米涂层后其任一界面可暴露于水环境，霉菌环境，酸、碱性溶剂环境，酸、碱性盐雾环境，酸性大气环境，有机溶剂浸泡环境，化妆品环境，汗液环境，冷热循环冲击环境或湿热交变环境中使用。
  4. 根据权利要求1所述的一种具有调制结构的高绝缘纳米防护涂层的制备方法，其特征在于：所述步骤(1)中反应腔室为旋转体形腔室或者立方体形腔室，其容积为50～1000L，反应腔室的温度控制在30～60℃，所述惰性气体通入流量为5～300sccm。
  5. 根据权利要求1所述的一种具有调制结构的高绝缘纳米防护涂层的制备方法，其特征在于：所述步骤(2)中：通入单体A蒸汽、通入单体B蒸汽或通入单体C蒸汽，等离子体放电，进行化学气相沉积，沉积过程中等离子体放电过程包括小功率连续放电、脉冲放电或周期交替放电。
  6. 根据权利要求5所述的一种具有调制结构的高绝缘纳米防护涂层的制备方法，其特征在于：所述沉积过程中等离子体放电过程为小功率连续放电，具体包括以下沉积过程至少一次：
    沉积过程包括预处理阶段和镀膜阶段，预处理阶段等离子体放电功率为150～600W，持续放电时间60～450s，然后进入镀膜阶段，调整等离子体放电功率为10～150W，持续放电时间600～3600s。
  7. 根据权利要求5所述的一种具有调制结构的高绝缘纳米防护涂层的制备方法，其特征在于：所述沉积过程中等离子体放电过程为脉冲放电，具体包括以下沉积过程至少一次：
    沉积过程包括预处理阶段和镀膜阶段，预处理阶段等离子体放电功率为150～600W，持续放电时间60～450s，然后进入镀膜阶段，镀膜阶段为脉冲放电，功率10～300W，时间600s～3600s，脉冲放电的频率为1～1000HZ，脉冲的占空比为1:1～1:500。
  8. 根据权利要求5所述的一种具有调制结构的高绝缘纳米防护涂层的制备方法，其特征在于：所述沉积过程中等离子体放电过程为周期交替放电，具体包括以下沉积过程至少一次：
    沉积过程包括预处理阶段和镀膜阶段，预处理阶段等离子体放电功率为150～600W，持续放电时间60～450s，然后进入镀膜阶段，镀膜阶段等离子体为周期交替变化放电输出，功率10～300W，时间600s～3600s，交变频率为1-1000Hz，等离子体周期交替变化放电输出波形为锯齿波形、正弦波形、方波波形、全波整流波形或半波整流波形。
  9. 根据权利要求1所述的一种具有调制结构的高绝缘纳米防护涂层的制备方法，其特征在于：
    所述低偶极矩有机物单体包括：
    对二甲苯、苯、甲苯、四氟化碳、α-甲基苯乙烯、聚对二氯甲苯、二甲基硅氧烷、分子量500-50000的聚二甲基硅氧烷、烯丙苯、十氟联苯、十氟联苯酮、全氟烯丙基苯、四氟乙 烯、六氟丙烯、1H,1H-全氟辛基胺、全氟碘代十二烷、全氟三丁胺、1,8-二碘代全氟辛烷、全氟己基碘烷、全氟碘代丁烷、全氟碘代癸烷、全氟辛基碘烷、1,4-二(2',3'-环氧丙基)全氟丁烷、十二氟-2-甲基-2-戊烯、2-(全氟丁基)乙基甲基丙烯酸酯、2-(全氟辛基)乙基甲基丙烯酸酯、2-(全氟辛基)碘代乙烷、全氟癸基乙基碘、1,1,2,2-四氢全氟己基碘、全氟丁基乙烯、1H,1H,2H-全氟-1-癸烯、2,4,6-三(全氟庚基)-1,3,5-三嗪、全氟己基乙烯、3-(全氟正辛基)-1,2-环氧丙烷、全氟环醚、全氟十二烷基乙烯、全氟十二烷基乙基碘、二溴对二甲苯、1,1,4,4-四苯基-1,3-丁二烯；
    所述单官能度不饱和氟碳树脂包括：
    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、(全氟环己基)甲基丙烯酸酯、3,3,3-三氟-1-丙炔、1-乙炔基-3,5-二氟苯或4-乙炔基三氟甲苯；
    所述含双键、Si-Cl、Si-O-C、Si-N-Si、Si-O-Si结构或环状结构的有机硅单体包括：
    含双键结构的有机硅单体：烯丙基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三甲基硅烷、3-丁烯基三甲基硅烷、乙烯基三丁酮肟基硅烷、四甲基二乙烯基二硅氧烷、1,2,2-三氟乙烯基三苯基硅烷；
    含Si-Cl键的有机硅单体：三苯基氯硅烷、甲基乙烯基二氯硅烷、三氟丙基三氯硅烷、三氟丙基甲基二氯硅烷、二甲基苯基氯硅烷、三丁基氯硅烷、苄基二甲基氯硅烷；
    含Si-O-C结构的有机硅单体：四甲氧基硅烷、三甲氧基氢硅氧烷、正辛基三乙氧基硅烷、苯基三乙氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷、三乙基乙烯基硅烷、六乙基环三硅氧烷、3-(甲基丙烯酰氧)丙基三甲氧基硅烷、苯基三(三甲基硅氧烷基)硅烷、二苯基二乙氧基硅烷、十二烷基三甲氧基硅烷、正辛基三乙氧基硅烷、二甲氧基硅烷、3-氯丙基三甲氧基硅烷；
    含Si-N-Si或Si-O-Si结构的有机硅单体：六甲基二硅烷基胺、六甲基环三硅烷氨基、六甲基二硅氮烷、六甲基二硅醚；
    含环状结构的有机硅单体：六甲基环三硅氧烷、八甲基环四硅氧烷、六苯基环三硅氧烷、十甲基环五硅氧烷、八苯基环四硅氧烷、三苯基羟基硅烷、二苯基二羟基硅烷、铬酸双(三苯甲基硅烷基)酯、三氟丙基甲基环三硅氧烷、2,2,4,4-四甲基-6,6,8,8-四苯基环四硅氧烷、四甲基四乙烯基环四硅氧烷、3-缩水甘油醚氧基丙基三乙氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷；
    所述多官能度不饱和烃及烃类衍生物包括：
    1,3-丁二烯、异戊二烯、1,4-戊二烯、乙氧基化三羟甲基丙烷三丙烯酸酯、二缩三丙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、二丙烯酸乙二醇酯、二乙二醇二乙烯基醚或二丙烯酸新戊二醇酯。
  10. 根据权利要求1所述的一种具有调制结构的高绝缘纳米防护涂层的制备方法，其特 征在于：所述步骤(2)中，等离子体放电方式为射频放电、微波放电、中频放电、高频放电、电火花放电，所述高频放电和中频放电的波形为正弦或双极脉冲。
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EP3674438A4 (en) 2020-09-02
EP3674438B1 (en) 2023-03-29
EP3674438A1 (en) 2020-07-01
CN107587120A (zh) 2018-01-16
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