CN107587119B

CN107587119B - A kind of preparation method of the high insulating rigid nano protecting coating of composite construction

Info

Publication number: CN107587119B
Application number: CN201710729416.0A
Authority: CN
Inventors: 宗坚
Original assignee: Jiangsu Favored Nanotechnology Co Ltd
Current assignee: Jiangsu Favored Nanotechnology Co Ltd
Priority date: 2017-08-23
Filing date: 2017-08-23
Publication date: 2018-11-13
Anticipated expiration: 2037-08-23
Also published as: CN107587119A; WO2019037447A1

Abstract

A kind of preparation method of the high insulating rigid nano protecting coating of composite construction, belong to technical field of plasma, in this method, by reaction chamber suction, and it is passed through inert gas, so that base material is generated movement, filters out with low dipole moment and high chemically inert organic silicon monomer, regulate and control the free volume and compactness of coating by polyfunctional monomer so that coating has high-insulativity, excellent protective and wearability simultaneously.Organic silicon coating is deposited on high-insulativity coating, and carries out the hard processing on surface, forms the hard coat of compact texture, and the coating of the invention coating more existing than Parylene etc. under same thickness has superior barrier propterty, insulation performance and wearability.It solves at present using the problems such as coating abrasion performance existing for the coatings such as Parylene is insufficient, thickness is too thick, low production efficiency, hardening processing increases complex abrasion-proof silicon dioxide structure in coating, effectively increases the hardness and wearability of coating.

Description

A kind of preparation method of the high insulating rigid nano protecting coating of composite construction

Technical field

The invention belongs to plasma chemical vapor deposition technique fields, and in particular to arrive a kind of system of nano protecting coating Preparation Method.

Background technology

Mould proof, moisture proof, salt spray proof (abbreviation three proofings) are that electronic device needs to solve during storage, transport and use Major issue certainly.And mould, salt fog and humidity are typically resulted in electronic device and are failed due to short circuit.Further, since in life Many electronic products be easy touched and scraped in use, cause it to be destroyed.Therefore, for being applied to electronics The protective coating of industry, in addition to excellent " three proofings " performance, it is necessary to have good insulating properties and preferable wearability.

It is the effective ways for improving electronic product service life currently, being protected electronic product using protective coating. Obtaining protective coating, usually there are two types of method, liquid phase method and vapor phase methods.Liquid phase method generally use three-proofing coating carries out electronic product After coating, using heat cure or photocuring, one layer of fine and close organic coating is formed on circuit boards, is used for protection circuit plate and its phase Close erosion of the equipment from environment.Three-proofing coating has good high and low temperature resistance；At layer of transparent protective film, tool after its solidification There are the performances such as superior insulation, moisture-proof, anticreep, shockproof, dust-proof, anticorrosion, anti-aging, Inverter fed motor.But liquid phase process can produce Raw waste water, exhaust gas and waste liquid, the solvent used can generate electronic device substrate itself certain damage, its thickness is mostly in addition Tens microns, it is difficult to which control radiates for some needs and the electronic device function of signal transmission has centainly in Nano grade It influences.

Gas phase rule includes the methods of vapor deposition, plasma gas phase deposition.Most typical vapor deposition coating is parylene coating, It is developed by U.S. Union Carbide Co. and is widely applied in electronic product protection.Parylene coating is one kind to two Paraxylene is first heated to 680 degrees Celsius by the polymer of toluene, active paraxylene dimer is formed, in deposit cavity After reducing temperature, this dimer is deposited on electronic product surface, forms thin polymer film.Due to paraxylene structure height pair Claim, dipole moment 0, and due to the presence of phenyl ring, polymer molecule has larger free volume；Simultaneously because polymer molecule It measures relatively large so that coating compactness is high.Due to features above, parylene coating has low water, gas permeability, high barrier Effect can have the function that moisture-proof, waterproof, antirust, antiacid caustic corrosion.This Parylene is to deposit under vacuum conditions It generates, the protection in the field that liquid coating can not be related to such as high-frequency circuit, pole light current streaming system can be applied.Polymer thin Membrane coat thickness is the main reason for influencing Parylene vapor deposition conformal coat protection failure, and printed circuit board assembly is poly- It closes object film coating and local corrosion failure easily occurs in 3~7 micron thickness, thickness is applied in the case that not influencing high-frequency dielectric loss Degree answers >=30 microns.And the problems such as thick coating easily leads to weak heat-dissipating, signal obstructs, holiday increases.In addition, parylene coating The pre-processing requirements of printed wiring board for needing to protect are higher, such as conductive component, signal transmission assembly, radio frequency component Deng, needed when being vapor-deposited conformal coat to circuit board module do masking pretreatment, avoid impacting assembly property.This One drawback brings very big limitation to the application of parylene coating.Parylene coating prepares cost of material height, coating preparation condition Harsh (high temperature, condition of high vacuum degree requirement), rate of film build are low, it is difficult to extensive use.Further, since parylene coating hardness is relatively Low, usually less than H is easy to be scratched by external force and barrier propterty is caused to be destroyed under the conditions of meeting touch and scraping.

In view of the above problems, a kind of environmental protection of exploitation, good insulating, high rigidity, and with excellent under coating thinner case The coating and preparation method of barrier propterty have important application value.

Plasma activated chemical vapour deposition (plasma chemical vapor deposition, PCVD) be it is a kind of with etc. Gas ions activated reactive gas, promotion are chemically reacted in matrix surface or near surface space, generate the technology of solid film.Deng Gas ions chemical vapour deposition technique coating has the following advantages：

(1) it is dry process, it is uniformly pin-free generates film.

(2) chemistry such as the solvent resistance of plasma polymerization film, chemical resistance, heat resistance, abrasion resistance properties, physics Property is stablized.

(3) plasma polymerization film and matrix gluing are good.

(4) it may be made as uniform film in the substrate surface of concave-convex irregular.

(5) coating preparation temperature is low, can be carried out under normal temperature condition, effectively avoid the damage of temperature sensitive device.

(6) plasma process can not only prepare thickness and be micron-sized coating but also can prepare ultra-thin nanoscale Coating.

(7) designability of coating is strong, and under plasma conditions, most Orqanics Monomers can be activated to have The free radical of greater activity, and form coating on electronic product surface.To the sieve of monomer dipole moment, chemical inertness, free volume Choosing with design be obtain good insulating, under thinner case with excellent barrier propterty coating Critical policies.

(8) coating structure controllability is strong, can change the ingredient and ratio of monomer at any time so that coating have multilayer, gradient, The special constructions such as modulation.

(9) inorganic and organic composite structure coating can be prepared.

Currently, most of plasma coatings are traditional hydrocarbon oxygen organic compound, these traditional organic coatings are compared, Organic silicon coating has the characteristics that the feature of environmental protection, hardness are high, wearability is good, good insulating, electronic product sector application increasingly Extensively.Organic silicon monomer itself is nontoxic, and will not be decomposed into poisonous and harmful substance, after monomer polymerization, due to tool in polymer coating There is silicon oxygen bond or inorganic SiO can be formed in the coating₂Nano particle makes it have high hardness, good insulating properties and heat-resisting Performance.But current most of organic silicon coatings are obtained by liquid phase method.Rear shape is hydrolyzed in organic silicon monomer in the solution At colloidal sol, sol coating finally passes through heat cure on by processing exemplar, and one layer of dense coating is formed on model machine surface.Coating Thickness be usually several microns to what time micron.Liquid phase organic silicon coating technology than traditional liquid phase coating technology although have more preferable Environment-friendly type, but there is also many deficiencies：

(1) it needs to use water or organic matter as solvent, these solvents have an adverse effect to electronic product；

(2) it there are waste water, waste liquid and exhaust gas, is post-processed；

(3) coating layer thickness poor controllability, it is difficult to which Nano grade is arrived in control.

In addition, the organic coating of plasma-deposited acquisition at present, such as fluororine-carbon coating, Parylene coating coating, Its usual hardness is HB-2H, is easy to cause to damage under the conditions of touch and scraping, reduce the service life.

Invention content

The present invention provides a kind of preparation of the high insulating rigid nano protecting coating of composite construction to solve above-mentioned technical problem Method.In the preparation process, filters out with low dipole moment and high chemically inert organic silicon monomer, pass through polyfunctional monomer Regulate and control the free volume and compactness of coating so that coating has high-insulativity, excellent protective and wearability simultaneously.In height Organic silicon coating is deposited on insulating properties coating, and carries out the hard processing on surface, forms the hard coat of compact texture.

Since plasma chemical vapor deposition process may be not only suitable for various of monomer, and to the ingredient of the coating of formation with The controllability of structure is strong, therefore, by the design of monomer and the optimization of technological parameter, to coating composition and structure carry out regulation and control with It constructs, low dipole moment monomer and hard organosilicon monomer can be organically combined, be formed while there is high-insulativity and high rigidity Coating.This coating, under same thickness coating more existing than Parylene etc. have superior barrier propterty, insulation performance and Wearability.To effectively solve at present using problems existing for the coatings such as Parylene, too such as coating abrasion performance deficiency, thickness Thickness, low production efficiency, weak heat-dissipating, signal barrier etc.

The technical solution adopted in the present invention is as follows：

A kind of preparation method of the high insulating rigid nano protecting coating of composite construction, it is characterised in that：Include the following steps：

(1) pre-treatment：

Base material is placed in the reaction chamber of nano coating Preparation equipment, reaction chamber is continuously vacuumized, by reaction chamber Indoor vacuum degree is extracted into 10~200 millitorrs, and is passed through inert gas He, Ar or He and Ar mixed gas, opening movement mechanism, Base material is set to generate movement in reaction chamber；

(2) prepared by the high insulating coating of composite construction：

It is passed through in monomer A steam to reaction chamber, until vacuum degree is 30~300 millitorrs, opens plasma discharge, carry out Chemical vapor deposition prepares high insulating nano coating in substrate surface chemical vapor deposition, and stopping is passed through monomer A steam, is passed through Monomer B steam continues plasma discharge, carries out chemical vapor deposition, prepares organosilicon in high insulating nano coating surface and receive Rice coating, obtains the high insulating nano coating of composite construction, and stopping is passed through monomer B steam；

The monomer A vapor compositions include：

At least one low dipole moment Orqanics Monomer and at least one polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative it is mixed Object is closed, the mass fraction in the monomer A steam shared by polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative is 15~65%；

The monomer B vapor compositions include：

At least one organic silicon monomer containing double bond, Si-Cl, Si-O-C, Si-N-Si, Si-O-Si structure or cyclic structure With at least one polyfunctionality unsaturated hydrocarbons and the mixture of hydrocarbon derivative, polyfunctionality is unsaturated in the monomer B steam Mass fraction shared by hydrocarbon and hydrocarbon derivative is 15~65%；

It is to be atomized monomer by charge pump, volatilize and by 10~200 milli of low pressure to be passed through monomer A and monomer B steam Support introduces reaction chamber, and the flow for being passed through monomer A and monomer B is 10~1000 μ L/min；

(3) surface hard is handled：

It is passed through oxygen and/or vapor, flow is 10~100 μ L/min, and wherein oxygen can be in any proportion with vapor Mixing, plasma discharge power is 50-100W, continuous discharging time 60s-180s, to the high insulating nano of composite construction Coating surface carries out hard processing；

(4) it post-processes：

Stopping is passed through oxygen and/or vapor, is simultaneously stopped plasma discharge, persistently vacuumizes, and keeps reaction chamber Vacuum degree is 10~200 millitorrs, is passed through air to an atmospheric pressure after 1~5min, stops the movement of base material, then take out base material ?；

Alternatively, stopping being passed through oxygen and/or vapor, it is simultaneously stopped plasma discharge, sky is filled with into reaction chamber Then gas or inert gas are evacuated to 10-200 millitorrs to pressure 2000-5000 millitorrs, carry out above-mentioned inflation and vacuumize step Suddenly at least once, air is passed through to an atmospheric pressure, stops the movement of base material, then takes out base material.

Under low vacuum plasma discharge environment, by effective output to energy, keep monomer molecule structure more active Chemical bond be broken, form the higher free radical of activity, free radical passes through chemical bond with electronic product surface active group In conjunction with polymerization forms nano thin-film, finally forms high-insulativity protective coating in substrate surface.

Base material generates movement in reaction chamber in the step (1), and substrate transport form is base material relative response chamber It includes circular motion, ellipse circular motion, planetary motion, spherical surface to carry out straight reciprocating motion or curvilinear motion, the curvilinear motion Movement or the curvilinear motion of other irregular routes.

Base material is solid material in the step (1), and the solid material is electronic product, electric component, Electronic Assemblies Semi-finished product, pcb board, metallic plate, polytetrafluoroethylene (PTFE) plank or electronic component, and the substrate surface prepares organic silicon nano Its any interface can be exposed to water environment after coating, and mould environment, acid, basic solvent environment, acid, alkaline salt mist environment are acid Atmospheric environment, organic solvent impregnate environment, cosmetics environment, sweat environment, cold cycling shock environment or damp and hot alternation environment Middle use.

In the step (1) reaction chamber be rotator shaped chamber or cube shaped chamber, volume be 50~ 1000L, at 30~60 DEG C, it is 5~300sccm that the inert gas, which is passed through flow, for the temperature control of reaction chamber.

In the step (2)：It is passed through monomer A steam or monomer B steam, plasma discharge carries out chemical vapor deposition, Deposition process plasma discharge process includes small-power continuous discharge, pulsed discharge or period alternating discharge.

The deposition process plasma discharge process is small-power continuous discharge, specifically includes following deposition process extremely It is few primary：

Deposition process include pretreatment stage and plating mem stage, pretreatment stage plasma discharge power be 150~ 600W, 60~450s of continuous discharging time, subsequently into plating mem stage, adjustment plasma discharge power is 10~150W, is held Continuous 600~3600s of discharge time.

The deposition process plasma discharge process is pulsed discharge, specifically includes following deposition process at least one It is secondary：

Deposition process include pretreatment stage and plating mem stage, pretreatment stage plasma discharge power be 150~ 600W, 60~450s of continuous discharging time, subsequently into plating mem stage, plating mem stage be pulsed discharge, 10~300W of power, when Between 600s~3600s, the frequency of pulsed discharge is 1~1000HZ, and the duty ratio of pulse is 1:1~1:500.

The deposition process plasma discharge process is period alternating discharge, specifically includes following deposition process at least Once：

Deposition process include pretreatment stage and plating mem stage, pretreatment stage plasma discharge power be 150~ 600W, 60~450s of continuous discharging time, subsequently into plating mem stage, plated film phase plasma is period alternately variation electric discharge Output, 10~300W of power, time 600s~3600s, alternative frequency 1-1000Hz, the alternately variation electric discharge of plasma period Output waveform is zig-zag, sinusoidal waveform, square-wave waveform, current waveform in full-wave rectifier or half wave rectification wave.

The low dipole moment Orqanics Monomer includes：Paraxylene, toluene, carbon tetrafluoride, α-methylstyrene, gathers benzene To dichlorotoleune, dimethyl siloxane, the dimethyl silicone polymer of molecular weight 500-50000, phenyl allyloxy, decafluorobiphenyl, ten fluorine Biphenyl ketone, perfluorinated allyl base benzene, tetrafluoroethene, hexafluoropropene, 1H, 1H- perfluoro capryls amine, perfluor dodecyl iodides, perfluor three Butylamine, bis- iodo perfluorooctane of 1,8-, perfluoro-hexyl iodide alkane, perfluor butyl iodide, perfluor iodo decane, perfluoro octyl iodide alkane, 1,4- bis- (2', 3'- glycidyl) perfluorinated butane, 12 fluoro- 2- methyl -2- amylenes, 2- (perfluoro butyl) ethyl-methyl propylene Acid esters, 2- (perfluoro capryl) ethylmethyl acrylate, 2- (perfluoro capryl) iodic ether, perfluoro decyl ethyl iodide, 1,1,2, 2- tetrahydrochysenes perfluoro-hexyl iodide, perfluorobutyl ethylene, 1H, 1H, 2H- perfluor -1- decene, 2,4,6- tri- (perfluor heptyl) -1,3,5- Triazine, perfluorohexyl ethylene, 3- (n-perfluoro-octyl) -1,2 epoxy prapane, perfluoro-cyclicether, perfluorododecyl ethylene, perfluor Dodecyl ethyl iodide, dibromo paraxylene, 1,1,4,4- tetraphenyl -1,3- butadiene；

The organic silicon monomer packet containing double bond, Si-Cl, Si-O-C, Si-N-Si, Si-O-Si structure or cyclic structure It includes：

Organic silicon monomer containing double bond structure：Allyltrimethoxysilanis, vinyltriethoxysilane, vinyl three Methyl-monosilane, 3- cyclobutenyls trimethyl silane, vinyl tributyl ketoximyl silane, tetramethyl divinyl disiloxane, 1,2, 2- trifluoro vinyl tri-phenyl-silanes；

The organic silicon monomer of the key containing Si-Cl：Tri-phenyl chloride, methylvinyldichlorosilane, trifluoro propyl trichlorine silicon Alkane, trifluoropropylmethyldichlorosilane, 3,5-dimethylphenyl chlorosilane, tributyl chlorosilane, benzyl dimethyl chlorosilane；

The organic silicon monomer of the structure containing Si-O-C：Tetramethoxy-silicane, trimethoxy hydrogen siloxane, n-octyl triethoxy Silane, phenyl triethoxysilane, vinyl three (2- methoxy ethoxies) silane, triethylvinylsilane silane, Hexaethyl ring Trisiloxanes, 3- (methacryloxypropyl) propyl trimethoxy silicane, phenyl three (trimethylsiloxane group) silane, diphenyl two Ethoxysilane, dodecyltrimethoxysilane, n-octytriethoxysilane, dimethoxysilane, 3- chloropropyl front threes Oxysilane；

The organic silicon monomer of the structure containing Si-N-Si or Si-O-Si：Hexamethyldisilane base amine, three silane ammonia of pregnancy basic ring Base, hexamethyldisilazane, hexamethyldisiloxane；

Organic silicon monomer containing cyclic structure：Hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, three silicon of hexaphenyl ring Oxygen alkane, decamethylcyclopentaandoxane, octaphenylcyclotetrasiloxane, triphenyl silicol, Diphenylsilanediol, chromic acid are double (trityl silylation) ester, trifluoro propyl methyl cyclotrisiloxane, four silicon of 2,2,4,4- tetramethyl -6,6,8,8- tetraphenyls ring Oxygen alkane, t etram-ethyltetravinylcyclotetrasiloxane, 3- glycidyl ether oxypropyltriethoxysilanes, γ-glycidol ether Oxygen propyl trimethoxy silicane；

The polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative include：

1,3- butadiene, isoprene, 1,4- pentadienes, ethoxylated trimethylolpropane triacrylate, two contractings three Propylene glycol diacrylate, polyethyleneglycol diacrylate, 1,6 hexanediol diacrylate, ethylene glycol diacrylate, two Ethylene glycol divinyl ether or diacrylic acid pentyl diol ester.

In the step (2), the plasma discharge manner is radio frequency discharge, microwave discharge, intermediate frequency discharges, high frequency is put The waveform of electricity, spark discharge, the high-frequency discharge and intermediate frequency electric discharge is sinusoidal or bipolar pulse, and radio frequency plasma is to utilize Electromagnetic field of high frequency is discharged and the plasma of generation.Microwave method is the energy excitation plasma using microwave, has energy profit With efficient advantage, simultaneously because electrodeless discharge, plasma is pure, is current high quality, high-speed, large area preparation Excellent process.

In coating preparation process, kinetic characteristic and plasma discharge energy the combination linkage of base material.Preparation process is medium While plasma discharge, base material generates movement, improves coating deposition efficiency, and improve uniformity and the cause of coating layer thickness Close property.

Prepared coating has insulation, waterproof and dampproof, mould proof, acid and alkali resistance solvent, acid and alkali resistance salt fog acidproof Property air, organic solvent-resistant impregnate, resistance to cosmetics, resistance to sweat, cold-resistant thermal cycle impact (- 40 DEG C~+75 DEG C), wet-heat resisting alternation Characteristics such as (humidity 75%~95%).While having above-mentioned barrier propterty, coating layer thickness is in 1~1000nm, to frequency The influence of radio frequency communication signal of the rate within the scope of 10M~8G is less than 5%.

The above-mentioned technical proposal of the present invention has the following advantages compared with prior art：

1, plasma chemical vapor deposition technique method, it is more more environmentally friendly than liquid phase method three proofings coating coating method；And it compares Parylene method is deposited, depositing temperature is low, speed faster, the controllability of coating structure and ingredient it is strong, the alternative of monomer is strong.

2, base material moves in reaction chamber, and the base material coating film thickness of different location is made to tend to consistent, solve by Lead to the non-uniform problem of substrate surface coating layer thickness in different zones monomer density difference in reaction chamber.In preparation process, Kinetic characteristic and plasma discharge energy the combination linkage of base material, while discharge energy exports, base material is moved, and is improved Deposition efficiency, so as to get protective coating compactness significantly improve.Simultaneously because the raising of deposition efficiency, the change of monomer vapours Learn monomer raw material dosage also only other in the prior art dosage 10%~15%, to reduce the row of tail gas exhaust It puts, it is more environmentally protective, it is of great significance in improving actual production efficiency.

3, the present invention is filtered out with low dipole moment and high chemically inert Orqanics Monomer, passes through polyfunctional monomer tune Control the free volume and compactness of coating so that coating has high-insulativity, high rigidity and excellent protective simultaneously.

(1) present invention selects have high symmetry phenyl ring and its benzene derivative or perfluorochemical as monomer, polymerization Molecule is coated by a large amount of fluorine atoms due to symmetrical or each carbon atom afterwards, and polarity is relatively low, and dielectric constant is very low, is less than 2.8, Insulating properties is high；

(2) since benzene ring structure and fluorine carbon structure have higher chemical inertness, the polymer formed has excellent Chemical stability；

(3) by the length and degree of functionality of cross-linker molecules chain, the compactness and free volume of coating can be effectively improved, from And improve insulating properties and protective.

(4) by the other monomers of introducing crosslinked structure, monomer ratio is controlled, according to the molecular bond energy of different monomers, key The difference of long difference, vapourizing temperature gives the Significant Change of the output of equipment corresponding energy and technological parameter, obtain it is compound, The polymer nanocomposite coating of grading structure both ensure that the exhausted of film if parylene layer and hard organosilicon layer are compound Edge, and improve the environmental corrosion resisting and abrasion resistance properties of the products such as electronic product.

(5) hardening handle, increase complex abrasion-proof silicon dioxide structure in coating, effectively increase coating hardness and Wearability.

4, compared to traditional single functionality Orqanics Monomer, under plasma conditions, connecting with silicon in organic silicon monomer Condensation reaction can occur between each other for the functional group connect, therefore, solid netted crosslinking can occur between monomer and monomer, can be into One step improves compactness, wearability and the corrosion resistance of coating.

It is substituted using the organic silicon monomer containing double bond, Si-Cl, Si-O-C, Si-N-Si, Si-O-Si structure or cyclic structure The hydrocarbon oxygen organic compound monomer of traditional single functionality, under plasma condition, since the functional group being connected with silicon all has Higher reactivity, therefore, these organic silicon monomers have more cross-linking active sites；

Since the functional group being connected with silicon in organic silicon monomer is easy to happen hydrolysis or alcoholysis, obtained structure is very easy to Condensation reaction occurs, and is cross-linked with each other, each silicon atom at least provides 1-4 active site, has higher activity, therefore, It is easier to generate free radical in low-temperature plasma and cross-linking reaction occurs, form fine and close cross-linking compounds, improve anti- Protect performance.Plasma deposition method coating layer thickness can realize controllable precise from nanometer to micron, and need not use solvent, The deficiencies of liquid phase organic silicon coating method generates waste water, waste liquid, exhaust gas is also avoided simultaneously.

5, in surface hard processing procedure, the introducing portion oxygen in monomer so that oxygen occurs for oxygen and organic silicon monomer Change reaction, when oxygen replaces the carbon on silicon atom completely, organosilicon can be oxidized to nano silicon dioxide.Water is introduced in monomer Steam then can occur hydrolysis with organosilicon, produce nano silicon dioxide.Obtained nano silicon dioxide mass percent is about For 5%-20%；Since silica is atomic crystal, hardness is up to 1500Hv, is dispersed in coating, since disperse is strong Change effect, is greatly improved coating hardness.The usual hardness of organic coating of plasma-deposited acquisition is HB-2H, when in coating When silica quality percentage is 5%, coating hardness can be by the H-3H that is increased to, when silica quality percentage in coating It is 20%, coating hardness is increased to 2H-4H.

Electronic equipment in daily life is easily damaged by the erosion of corrosive environment, is substantially at during use In corrosive environment, if things go on like this, the damages such as electronic equipment short circuit and open circuit can be caused.The film plating process of patent of the present invention increases Nanometer has been added to be of great significance in improving actual production efficiency.Improve coating corrosive environment service life, Improve the protecting effect of product.It is mainly used in following product：

(1), portable equipment keyboard：Portable keyboard has the characteristics that small and light, is usually used in computer, the equipment such as mobile phone. It can handle official business convenient for user in route.But when it encounters the pollution of common liquid, the unexpected of the teacup that is such as filled with water overturns, rain Water, sweat are impregnated with, and keyboard is easy short circuit, and then damages.After carrying out plated film to it using such nano coating, when can Ensure surface of keyboard easy to clean, function is intact after meeting water so that keyboard can adapt to more acute environment.

(2), LED display：LED display has demonstration, StoreFront decoration, illumination, the purposes such as warning.Its partial use The adverse circumstances in face of rainwater or more dust are needed, when such as rainy day, the outdoor LED advertisement screen curtain in market, road surface warning lamp, life The LED display control panel in workshop is produced, these adverse circumstances lead to LED screen failure, and are easy dust stratification, not easy cleaning, After the nano coating, the above problem can effectively solve the problem that.

(3), intelligent fingerprint lock：Fingerprint Lock is intelligent lock, it has gathered computer information technology, electronic technology, machinery Technology and modern five gold process, are widely used in police criminal detection and judicial domain.But after it meets water, inner wire Louis is short Road, it is difficult to repair, violence is needed to tear lock open, after the coating, this problem can be avoided.

(4), hearing aid, bluetooth headset：Hearing aid is with bluetooth headset without connection, after the coating, Yong Huke It to be used under water environment within a certain period of time, such as has a bath, on rainy day, equipment will not be infiltrated because of rainwater to be damaged.

(5), operative sensor：Operative sensor needs work in liquid environment, such as hydraulic pressure, oil pressure sensor, and The sensor and working environment used in underwater operation equipment often meet the sensor of water, these sensors are using the painting After layer, can ensure will not lead to faulty sensor because of liquid intrusion mechanical equipment internal structure.

(6), most of 3C Products：Such as mobile phone, notebook, PSP.

(7), other equipment for needing waterproof：Including needs operation in wet environment, or it is likely encountered common liquid It splashes and waits fortuitous events, the equipment of internal light current circuit normal operation can be influenced.

The high insulating rigid coating of composite construction prepared by this method can be applicable to following different environment and its be related to Related product：

It is waterproof and dampproof mould proof：

1 house interior trim：Toilet top surface, wallpaper, pendent lamp, curtain, window screening.2 daily necessitiess：Mosquito net, desk lamp cover, chopsticks Basket, automobile rearview mirror.3 historical relics and the art work：Copybook, antiques, woodcarving, leather, bronze ware, silk, ancient costume, ancient books.4 electronics member Device and electronic product：Sensor (operation in moist or dirty environment), each electronic product (electronic sphygmomanometer, intelligent hand Table) chip, wiring board, mobile phone, LED screen, hearing aid.5 precision instruments and optical device：Mechanical watch, microscope.

Acid and alkali resistance solvent, acid and alkali resistance salt fog, acid resistance air：

1 house inside gadget：Wallpaper, ceramic tile.2 safety devices：Acidproof (alkali) gloves, acidproof (alkali) protective garment.3 mechanical equipments And pipeline：Flue desulfurization equipment, sealing element (acid/base lubricating oil), pipeline, valve, Large Diameter Pipeline sea conveyance conduit liner etc. Place.4 various reaction kettles, reactor.The production of 5 chemicals, storage；Sewage disposal, aeration tank；6 is other：Soda acid workshop, alkali prevention The every profession and trades such as aerospace, electricity power, Ferrous Metallurgy, petrochemical industry, medical treatment, storage container, statue (reduce acid rain to its Corrosion), sensor (under acid/base environment).

Organic solvent-resistant impregnates, resistance to cosmetics, resistance to sweat：

1 such as alkane, alkene, alcohol, aldehyde, amine, ester, ether, ketone, aromatic hydrocarbon, hydrogenate hydrocarbon, terpene hydrocarbon, halogenated hydrocarbons, jeterocyclic chemistry Object, nitrogenous compound and sulfur-containing compound solvent etc.；2 toiletry bag packaging containers；3 Fingerprint Locks, earphone.

Cold-resistant thermal cycle impact (- 40 DEG C~+75 DEG C), wet-heat resisting alternation (humidity 75%~95%)：Electrician, electronics, vapour Vehicle electric appliance, such as aviation, automobile, household electrical appliances, scientific research field equipment.

Specific implementation mode

With reference to specific embodiment, the present invention will be described in detail, but the invention is not limited in specific embodiments.

Embodiment 1

A kind of preparation method of the high insulating rigid nano protecting coating of composite construction, includes the following steps：

(1) pre-treatment：

Base material is placed in the reaction chamber of nano coating Preparation equipment, closed reaction chamber simultaneously continuously takes out reaction chamber The indoor vacuum degree of reaction chamber is extracted into 10 millitorrs, is passed through inert gas Ar by vacuum, and opening movement mechanism makes base material react Movement is generated in chamber；

Base material is solid material in step (1), and the solid material is blocky aluminum material and pcb board, and the base material Its any interface can be exposed in hot and cold loop test environment after surface prepares cold-resistant thermal cycle impact coating.

Reaction chamber is rotator shaped chamber in step (1), and the volume of reaction chamber is 50L, the temperature control of reaction chamber For system at 30 DEG C, the flow for being passed through inert gas is 5sccm.

Base material generates movement in reaction chamber in step (1), and substrate transport form carries out for base material relative response chamber Circular motion, rotating speed are 10 turns/min.

(2) prepared by the high insulating coating of composite construction：

It is passed through in monomer A steam to reaction chamber, until vacuum degree is 30 millitorrs, opens plasma discharge, carry out chemistry Vapor deposition prepares high insulating nano coating in substrate surface chemical vapor deposition, and stopping is passed through monomer A steam, is passed through monomer B Steam continues plasma discharge, carries out chemical vapor deposition, and preparing organic silicon nano in high insulating nano coating surface applies Layer, obtains the high insulating nano coating of composite construction, and stopping is passed through monomer B steam；

The monomer A vapor compositions include：

A kind of mixture of low dipole moment Orqanics Monomer and three kinds of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative, it is described Mass fraction in monomer A steam shared by polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative is 15%；

A kind of low dipole moment Orqanics Monomer is：Perfluorinated allyl base benzene,

Three kinds of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative are：1,4- pentadienes, two propylene of tripropylene glycol Acid esters, 1,6- hexanediyl esters,

The monomer B vapor compositions include：

The mixture of three kinds of organic silicon monomers and a kind of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative containing double bond structure, Mass fraction in the monomer B steam shared by polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative is 65%；

Three kinds of organic silicon monomers containing double bond structure are：Vinyltriethoxysilane, 3- cyclobutenyl trimethyl silicanes Alkane, vinyl tributyl ketoximyl silane,

The mixture of a kind of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative is：Ethoxylated trimethylolpropane three Acrylate,

It is to be atomized monomer by charge pump, volatilize and introduced by 10 millitorr of low pressure to be passed through monomer A and monomer B steam Reaction chamber, the flow for being passed through monomer A and monomer B are 10 μ L/min；

Monomer A steam or monomer B steam are passed through in the step (2), plasma discharge carries out chemical vapor deposition, Deposition process plasma discharge process is small-power continuous discharge, and it is primary to specifically include following deposition process：

Deposition process includes pretreatment stage and plating mem stage, and pretreatment stage plasma discharge power is 150W, is held Continuous discharge time 450s, subsequently into plating mem stage, adjustment plasma discharge power is 10W, continuous discharging time 3600s.

In the step (2), plasma discharge manner is radio frequency discharge；

(3) surface hard is handled：

It is passed through oxygen, flow is 10 μ L/min, and plasma discharge power is 50W, continuous discharging time 180s, to multiple The high insulating nano coating surface for closing structure carries out hard processing；

(4) it post-processes：

Stopping is passed through oxygen, is simultaneously stopped plasma discharge, persistently vacuumizes, and it is 10 millis to keep reaction chamber vacuum degree It holds in the palm, is passed through air to an atmospheric pressure after 1min, then takes out base material.

The coating dielectric constant that the above process obtains is 2.73, hardness 2H, aluminum material and pcb board after plated film, cold, It is as follows that thermal cycle impact tests effect：

Aluminum material after above-mentioned plated film, damp and hot alternation test effect are as follows：

Embodiment 2

(1) base material is placed in nano coating Preparation equipment reaction chamber, closed reaction chamber is simultaneously continuous to reaction chamber It vacuumizes, the indoor vacuum degree of reaction chamber is extracted into 30 millitorrs, be passed through inert gas He, start motion, base material is made to carry out Movement；

Base material is solid material in step (1), and the solid material is blocky aluminum material, and prepared by the substrate surface Its any interface can be exposed in damp and hot test environment after wet-heat resisting alternation coating.

Reaction chamber is cube shaped chamber in step (1), and the volume of reaction chamber is 280L, the temperature control of reaction chamber For system at 42 DEG C, the flow for being passed through inert gas is 19sccm.

Base material carries out planetary motion in step (1), and revolution speed is 12 turns/min, and rotational velocity is 8 turns/min.

(2) prepared by the high insulating coating of composite construction：

It is passed through in monomer A steam to reaction chamber, until vacuum degree is 70 millitorrs, opens plasma discharge, carry out chemistry Vapor deposition prepares high insulating nano coating in substrate surface chemical vapor deposition, and stopping is passed through monomer A steam, is passed through monomer B Steam continues plasma discharge, carries out chemical vapor deposition, and preparing organic silicon nano in high insulating nano coating surface applies Layer, obtains the high insulating nano coating of composite construction, and stopping is passed through monomer B steam；

The monomer A vapor compositions include：

The mixture of five kinds of low dipole moment Orqanics Monomers and a kind of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative, it is described Mass fraction in monomer A steam shared by polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative is 65%；

Five kinds of low dipole moment Orqanics Monomers are：Phenyl allyloxy, decafluorobiphenyl ketone, tetrafluoroethene, 1H, 1H- perfluors are pungent Base amine, perfluor dodecyl iodides,

A kind of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative are：Tri (propylene glycol) diacrylate,

The monomer B vapor compositions include：

A kind of mixing of the organic silicon monomer and three kinds of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative of the structure containing Si-Cl Object, the mass fraction in the monomer B steam shared by polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative is 15%；

A kind of organic silicon monomer of structure containing Si-Cl is：Trifluoropropylmethyldichlorosilane,

The mixture of three kinds of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative is：Isoprene, tripropylene glycol Diacrylate, polyethyleneglycol diacrylate,

It is to be atomized monomer by charge pump, volatilize and introduced by 30 millitorr of low pressure to be passed through monomer A and monomer B steam Reaction chamber, the flow for being passed through monomer A and monomer B are 150 μ L/min；

Monomer A steam or monomer B steam are passed through in the step (2), plasma discharge carries out chemical vapor deposition, Deposition process plasma discharge process is small-power continuous discharge, specifically includes following deposition process six times：

Deposition process includes pretreatment stage and plating mem stage, and pretreatment stage plasma discharge power is 600W, is held Continuous discharge time 60s, subsequently into plating mem stage, adjustment plasma discharge power is 150W, continuous discharging time 600s.

In the step (2), plasma discharge manner is microwave discharge；

(3) surface hard is handled：

It is passed through vapor, flow is 30 μ L/min, and plasma discharge power is 70W, continuous discharging time 80s, right The high insulating nano coating surface of composite construction carries out hard processing；

(4) it post-processes：

Stopping is passed through vapor, is simultaneously stopped plasma discharge, persistently vacuumizes, and it is 60 to keep reaction chamber vacuum degree Millitorr is passed through air to an atmospheric pressure after 2min, then takes out base material.

The coating dielectric constant that the above process obtains is 2.45, hardness 3H, after aluminum material plated film, cold cycling impact It is as follows to test effect：

Embodiment 3

(1) base material is placed in nano coating Preparation equipment reaction chamber, closed reaction chamber is simultaneously continuous to reaction chamber It vacuumizes, the indoor vacuum degree of reaction chamber is extracted into 80 millitorrs, be passed through the mixed gas of inert gas Ar and He, start fitness machine Structure makes base material be moved；

Base material is solid material in step (1), and the solid material is blocky polyfluortetraethylene plate and electric component, and institute The survey of GJB150.10A-2009 moulds can be exposed to by stating its any interface after blocky polytetrafluoroethylene (PTFE) plate surface prepares mould proof coating Test ring uses in border, its any interface can be exposed to International Industry after the electric component surface prepares waterproof electrical breakdown withstand coating Environment described in waterproofing grade standard IPX7 uses.

Reaction chamber is rotator shaped chamber in step (1), and the volume of reaction chamber is 430L, the temperature control of reaction chamber For system at 46 DEG C, the flow for being passed through inert gas is 54sccm.

Base material carries out circular motion in step (1), and rotating speed is 15 turns/min.

(2) prepared by the high insulating coating of composite construction：

It is passed through in monomer A steam to reaction chamber, until vacuum degree is 120 millitorrs, opens plasma discharge, carry out chemistry Vapor deposition prepares high insulating nano coating in substrate surface chemical vapor deposition, and stopping is passed through monomer A steam, is passed through monomer B Steam continues plasma discharge, carries out chemical vapor deposition, and preparing organic silicon nano in high insulating nano coating surface applies Layer, obtains the high insulating nano coating of composite construction, and stopping is passed through monomer B steam；

The monomer A vapor compositions include：

The mixture of four kinds of low dipole moment Orqanics Monomers and three kinds of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative, it is described Mass fraction in monomer A steam shared by polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative is 57%；

Four kinds of low dipole moment Orqanics Monomers are：Toluene, decafluorobiphenyl ketone, 1,4- bis- (2', 3'- glycidyl) are complete Fluorine butane, 2- (perfluoro butyl) ethylmethyl acrylate,

Three kinds of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative are：1,3- butadiene, 1,4- pentadienes, polyethylene glycol Diacrylate,

The monomer B vapor compositions include：

The mixing of the organic silicon monomer and two kinds of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative of three kinds of structures containing Si-O-C Object, the mass fraction in the monomer B steam shared by polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative is 55%；

The organic silicon monomer of three kinds of structures containing Si-O-C is：Tetramethoxy-silicane, (the 2- methoxyl group ethoxies of vinyl three Base) silane, 3- (methacryloxypropyl) propyl trimethoxy silicane,

The mixture of described two polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative is：Isoprene, 1,6-HD two Acrylate,

It is to be atomized monomer by charge pump, volatilize and introduced by 80 millitorr of low pressure to be passed through monomer A and monomer B steam Reaction chamber, the flow for being passed through monomer A and monomer B are 360 μ L/min；

Monomer A steam or monomer B steam are passed through in the step (2), plasma discharge carries out chemical vapor deposition, The deposition process plasma discharge process is pulsed discharge, and it is primary to specifically include following deposition process：

Deposition process includes pretreatment stage and plating mem stage, and pretreatment stage plasma discharge power is 150W, is held Continuous discharge time 450s, subsequently into plating mem stage, plating mem stage is pulsed discharge, power 10W, time 3600s, pulsed discharge Frequency be 1HZ, the duty ratio of pulse is 1:500；

In the step (2), plasma discharge manner is spark discharge；

(3) surface hard is handled：

It is passed through oxygen and vapor, flow is 50 μ L/min, plasma discharge power is 80W, and continuous discharging time is 100s carries out hard processing to the high insulating nano coating surface of composite construction；

(4) it post-processes：

Stopping is passed through oxygen and vapor, is simultaneously stopped plasma discharge, persistently vacuumizes, and keeps reaction chamber vacuum Degree is 100 millitorrs, is passed through air to an atmospheric pressure after 3min, then takes out base material.

The coating dielectric constant that the above process obtains is 2.46, hardness 2H, after polyfluortetraethylene plate plated film, GJB150.10A-2009 mould test results：

It prepares waterproof electrical breakdown withstand coating electric component and tests underwater soaking experimental result under different voltages：

7 waterproofing grade of IPX tests (underwater 1m submerging test 30min) result：

Embodiment 4

(1) base material is placed in nano coating Preparation equipment reaction chamber, closed reaction chamber is simultaneously continuous to reaction chamber It vacuumizes, the indoor vacuum degree of reaction chamber is extracted into 100 millitorrs, be passed through inert gas Ar, start motion, base material is made to carry out Movement；

The volume of reaction chamber is 780L in step (1), and the temperature of reaction chamber is controlled at 53 DEG C, is passed through inert gas Flow is 180sccm.

Base material carries out straight reciprocating motion, movement velocity 40mm/min in step (1).

(2) prepared by the high insulating coating of composite construction：

It is passed through in monomer A steam to reaction chamber, until vacuum degree is 180 millitorrs, opens plasma discharge, carry out chemistry Vapor deposition prepares high insulating nano coating in substrate surface chemical vapor deposition, and stopping is passed through monomer A steam, is passed through monomer B Steam continues plasma discharge, carries out chemical vapor deposition, and preparing organic silicon nano in high insulating nano coating surface applies Layer, obtains the high insulating nano coating of composite construction, and stopping is passed through monomer B steam；

The monomer A vapor compositions include：

The mixture of six kinds of low dipole moment Orqanics Monomers and four kinds of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative, it is described Mass fraction in monomer A steam shared by polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative is 42%；

Six kinds of low dipole moment Orqanics Monomers are：It is 3- (n-perfluoro-octyl) -1,2 epoxy prapane, perfluoro-cyclicether, complete Fluorine dodecyl vinyl, perfluorododecyl ethyl iodide, dibromo paraxylene, 1, Isosorbide-5-Nitrae, 4- tetraphenyls -1,3-butadiene,

Four kinds of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative are：1,3- butadiene, 1,4- pentadienes, 1,6- oneself two Alcohol diacrylate, ethylene glycol diacrylate；

The monomer B vapor compositions include：

The mixture of the organic silicon monomer and two kinds of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative of four kinds of cyclic structures, institute It is 36% to state the mass fraction in monomer B steam shared by polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative；

The organic silicon monomer of four kinds of cyclic structures is：Bis- (trityl silylation) esters of chromic acid, trifluoro propyl methyl Cyclotrisiloxane, 2,2,4,4- tetramethyls -6,6,8,8- tetraphenyl cyclotetrasiloxanes, t etram-ethyltetravinylcyclotetrasiloxane,

The mixture of described two polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative is：1,4- pentadienes, ethoxylation three Hydroxymethyl-propane triacrylate,

It is to be atomized monomer by charge pump, volatilize and drawn by 100 millitorr of low pressure to be passed through monomer A and monomer B steam Enter reaction chamber, the flow for being passed through monomer A and monomer B is 580 μ L/min；

Monomer A steam or monomer B steam are passed through in the step (2), plasma discharge carries out chemical vapor deposition, The deposition process plasma discharge process is pulsed discharge, specifically includes following deposition process five times：

Deposition process includes pretreatment stage and plating mem stage, and pretreatment stage plasma discharge power is 600W, is held Continuous discharge time 60s, subsequently into plating mem stage, plating mem stage is pulsed discharge, power 300W, time 600s, pulsed discharge Frequency be 1000HZ, the duty ratio of pulse is 1:1；

In the step (2), plasma discharge manner is high-frequency discharge, and the waveform of high-frequency discharge is sine；

(3) surface hard is handled：

It is passed through oxygen and vapor, flow is 80 μ L/min, and plasma discharge power is 90W, and continuous discharging time is 90s carries out hard processing to the high insulating nano coating surface of composite construction；

(4) it post-processes：

Stopping is passed through oxygen and vapor, is simultaneously stopped plasma discharge, persistently vacuumizes, and keeps reaction chamber vacuum Degree is 200 millitorrs, is passed through compressed air to an atmospheric pressure after 4min, then takes out base material.

The coating dielectric constant that the above process obtains is 2.48, hardness 2H, after polyfluortetraethylene plate plated film, GJB150.10A-2009 mould test results：

Embodiment 5

(1) base material is placed in nano coating Preparation equipment reaction chamber, closed reaction chamber is simultaneously continuous to reaction chamber It vacuumizes, the indoor vacuum degree of reaction chamber is extracted into 200 millitorrs, be passed through the mixed gas of inert gas Ar and He, start movement Mechanism makes base material be moved；

Base material is solid material in step (1), and the solid material is blocky aluminum material, and prepared by the substrate surface Its any interface can be exposed in acid, alkali test environment after acid and alkali resistance environment coating.

The volume of reaction chamber is 1000L in step (1), and the temperature of reaction chamber is controlled at 60 DEG C, is passed through inert gas Flow be 300sccm.

Base material carries out curved reciprocating movement, speed 60mm/min in step (1).

(2) prepared by the high insulating coating of composite construction：

It is passed through in monomer A steam to reaction chamber, until vacuum degree is 300 millitorrs, opens plasma discharge, carry out chemistry Vapor deposition prepares high insulating nano coating in substrate surface chemical vapor deposition, and stopping is passed through monomer A steam, is passed through monomer B Steam continues plasma discharge, carries out chemical vapor deposition, and preparing organic silicon nano in high insulating nano coating surface applies Layer, obtains the high insulating nano coating of composite construction, and stopping is passed through monomer B steam；

The monomer A vapor compositions include：

The mixture of three kinds of low dipole moment Orqanics Monomers and three kinds of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative, it is described Mass fraction in monomer A steam shared by polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative is 27%；

Three kinds of low dipole moment Orqanics Monomers are：Perfluorotributylamine, perfluor iodo decane, perfluoro octyl iodide alkane,

Three kinds of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative are：1,3- butadiene, 1,6-HD diacrylate Ester, ethylene glycol diacrylate；

The monomer B vapor compositions include：

The organic silicon monomer and two kinds of polyfunctionality unsaturated hydrocarbons and hydro carbons of two kinds of structures containing Si-N-Si or Si-O-Si spread out The mixture of biology, the mass fraction in the monomer B steam shared by polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative is 23%；

The organic silicon monomer of described two structures containing Si-N-Si or Si-O-Si is：Three silane amino of pregnancy basic ring, pregnancy Base disilazane,

The mixture of described two polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative is：Diethylene glycol divinyl ether, two Acrylic acid neopentyl glycol ester,

It is to be atomized monomer by charge pump, volatilize and drawn by 200 millitorr of low pressure to be passed through monomer A and monomer B steam Enter reaction chamber, the flow for being passed through monomer A and monomer B is 1000 μ L/min；

Monomer A steam or monomer B steam are passed through in the step (2), plasma discharge carries out chemical vapor deposition, The deposition process plasma discharge process is period alternating discharge, and it is primary to specifically include following deposition process：

Deposition process includes pretreatment stage and plating mem stage, and pretreatment stage plasma discharge power is 150W, is held Continuous discharge time 450s, subsequently into plating mem stage, plated film phase plasma is period alternately variation electric discharge output, power 10W, time 3600s, alternative frequency 1Hz, the plasma period, alternately variation electric discharge output waveform was zig-zag.

In the step (2), plasma discharge manner discharges for intermediate frequency, and the waveform of intermediate frequency electric discharge is bipolar pulse；

(3) surface hard is handled：

It is passed through oxygen, flow is 100 μ L/min, and plasma discharge power is 100W, continuous discharging time 60ss, right The high insulating nano coating surface of composite construction carries out hard processing；

(4) it post-processes：

Stopping is passed through oxygen, is simultaneously stopped plasma discharge, inert gas is filled with into reaction chamber to pressure 2000 Then millitorr is evacuated to 10 millitorrs, carry out above-mentioned inflation and vacuum step is primary, is passed through air to an atmospheric pressure, stops The only movement of base material, then takes out base material.

Aluminum material after the obtained coating of the above process and plated film, hardness 4H, test effect are as follows：

(2) organic solvent-resistant test result：(pass expressions are soaked for a period of time rear contact angle variation and are less than 5 °)

(3) acid, alkaline test result：(after indicating experiment a period of time corrosion phenomenon does not occur for pass)

Embodiment 6

(1) base material is placed in nano coating Preparation equipment reaction chamber, closed reaction chamber is simultaneously continuous to reaction chamber It vacuumizes, the indoor vacuum degree of reaction chamber is extracted into 140 millitorrs, be passed through inert gas Ar, start motion, base material is made to carry out Movement；

Step (1) base material is solid material, and the solid material is blocky aluminum material and electric component, and the base material Its any interface can be exposed in organic solvent test environment after surface prepares high-insulativity coating.

The volume of reaction chamber is 450L in step (1), and the temperature of reaction chamber is controlled at 47 DEG C, is passed through inert gas Flow is 150sccm.

(2) prepared by the high insulating coating of composite construction：

It is passed through in monomer A steam to reaction chamber, until vacuum degree is 220 millitorrs, opens plasma discharge, carry out chemistry Vapor deposition prepares high insulating nano coating in substrate surface chemical vapor deposition, and stopping is passed through monomer A steam, is passed through monomer B Steam continues plasma discharge, carries out chemical vapor deposition, and preparing organic silicon nano in high insulating nano coating surface applies Layer, obtains the high insulating nano coating of composite construction, and stopping is passed through monomer B steam；

The monomer A vapor compositions include：

The mixture of seven kinds of low dipole moment Orqanics Monomers and three kinds of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative, it is described Mass fraction in monomer A steam shared by polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative is 23%；

Seven kinds of low dipole moment Orqanics Monomers are：Tetrafluoroethene, 1H, 1H- perfluoro capryls amine, perfluor iodo 12 Alkane, perfluor butyl iodide, 1,4- bis- (2', 3'- glycidyl) perfluorinated butane, 12 fluoro- 2- methyl -2- amylenes, 2- (perfluor fourths Base) ethylmethyl acrylate,

Three kinds of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative are：1,4- pentadienes, ethoxylation trihydroxy methyl third Alkane triacrylate, ethylene glycol diacrylate；

The monomer B vapor compositions include：

The mixing of the organic silicon monomer and three kinds of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative of four kinds of structures containing Si-O-C Object, the mass fraction in the monomer B steam shared by polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative is 38%；

The organic silicon monomer of four kinds of structures containing Si-O-C is：Diphenyl diethoxy silane, dodecyl trimethoxy Base silane, n-octytriethoxysilane, dimethoxysilane,

The mixture of three kinds of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative is：Isoprene, 1,4- pentadienes, two Ethylene glycol divinyl ether, diacrylic acid pentyl diol ester,

It is to be atomized monomer by charge pump, volatilize and drawn by 140 millitorr of low pressure to be passed through monomer A and monomer B steam Enter reaction chamber, the flow for being passed through monomer A and monomer B is 800 μ L/min；

Monomer A steam or monomer B steam are passed through in the step (2), plasma discharge carries out chemical vapor deposition, The deposition process plasma discharge process is period alternating discharge, specifically includes following deposition process five times：

Deposition process includes pretreatment stage and plating mem stage, and pretreatment stage plasma discharge power is 600W, is held Continuous discharge time 60s, subsequently into plating mem stage, plated film phase plasma is period alternately variation electric discharge output, power 300W, time 600s, alternative frequency 1000Hz, the plasma period, alternately variation electric discharge output waveform was halfwave rectifier wave Shape.

In the step (2), plasma discharge manner is microwave discharge

(3) surface hard is handled：

It is passed through vapor, flow is 70 μ L/min, and plasma discharge power is 75W, continuous discharging time 125s, right The high insulating nano coating surface of composite construction carries out hard processing；

(4) it post-processes：

Stopping is passed through vapor, is simultaneously stopped plasma discharge, and air is filled with into reaction chamber to 5000 milli of pressure Support, is then evacuated to 200 millitorrs, carries out above-mentioned inflation and vacuum step six times, is passed through air to an atmospheric pressure, stops The movement of base material, then takes out base material.Aluminum material after above-mentioned plated film, hardness 3H, other performance test effects are such as Under：

(1) hydro-oleophobicity

(2) electric component after above-mentioned plated film tests underwater soaking experimental result under different voltages：

(3) organic solvent-resistant test result：(pass expressions are soaked for a period of time rear contact angle variation and are less than 5 °)

(4) acid, alkaline test result：(after indicating experiment a period of time corrosion phenomenon does not occur for pass)

Claims

1. a kind of preparation method of the high insulating rigid nano protecting coating of composite construction, it is characterised in that：Include the following steps：

(1) pre-treatment：

Base material is placed in the reaction chamber of nano coating Preparation equipment, reaction chamber is continuously vacuumized, it will be in reaction chamber Vacuum degree be extracted into 10~200 millitorrs, and be passed through inert gas He, Ar or He and Ar mixed gas, opening movement mechanism makes base Material generates movement in reaction chamber；

(2) prepared by the high insulating coating of composite construction：

It is passed through in monomer A steam to reaction chamber, until vacuum degree is 30~300 millitorrs, opens plasma discharge, carry out chemistry Vapor deposition prepares high insulating nano coating in substrate surface chemical vapor deposition, and stopping is passed through monomer A steam, is passed through monomer B Steam continues plasma discharge, carries out chemical vapor deposition, and preparing organic silicon nano in high insulating nano coating surface applies Layer, obtains the high insulating nano coating of composite construction, and stopping is passed through monomer B steam；

The monomer A vapor compositions include：

The mixture of at least one low dipole moment Orqanics Monomer and at least one polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative, Mass fraction in the monomer A steam shared by polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative is 15~65%；

The monomer B vapor compositions include：

It is at least one containing double bond, the organic silicon monomer of Si-Cl, Si-O-C, Si-N-Si, Si-O-Si structure or cyclic structure and extremely The mixture of a kind of few polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative, in the monomer B steam polyfunctionality unsaturated hydrocarbons and Mass fraction shared by hydrocarbon derivative is 15~65%；

The flow for being passed through monomer A and monomer B is 10~1000 μ L/min；

Wherein, the low dipole moment Orqanics Monomer includes：Paraxylene, toluene, carbon tetrafluoride, α-methylstyrene, gathers benzene To dichlorotoleune, dimethyl siloxane, the dimethyl silicone polymer of molecular weight 500-50000, phenyl allyloxy, decafluorobiphenyl, ten fluorine Biphenyl ketone, perfluorinated allyl base benzene, tetrafluoroethene, hexafluoropropene, 1H, 1H- perfluoro capryls amine, perfluor dodecyl iodides, perfluor three Butylamine, bis- iodo perfluorooctane of 1,8-, perfluoro-hexyl iodide alkane, perfluor butyl iodide, perfluor iodo decane, perfluoro octyl iodide alkane, 1,4- bis- (2', 3'- glycidyl) perfluorinated butane, 12 fluoro- 2- methyl -2- amylenes, 2- (perfluoro butyl) ethyl-methyl propylene Acid esters, 2- (perfluoro capryl) ethylmethyl acrylate, 2- (perfluoro capryl) iodic ether, perfluoro decyl ethyl iodide, 1,1,2, 2- tetrahydrochysenes perfluoro-hexyl iodide, perfluorobutyl ethylene, 1H, 1H, 2H- perfluor -1- decene, 2,4,6- tri- (perfluor heptyl) -1,3,5- Triazine, perfluorohexyl ethylene, 3- (n-perfluoro-octyl) -1,2 epoxy prapane, perfluoro-cyclicether, perfluorododecyl ethylene, perfluor Dodecyl ethyl iodide, dibromo paraxylene, 1,1,4,4- tetraphenyl -1,3- butadiene；

1,3- butadiene, isoprene, 1,4- pentadienes, ethoxylated trimethylolpropane triacrylate, two contractings 3 the third two Alcohol diacrylate, polyethyleneglycol diacrylate, 1,6 hexanediol diacrylate, ethylene glycol diacrylate, diethyl two Alcohol divinyl ether or diacrylic acid pentyl diol ester；

The organic silicon monomer containing double bond, Si-Cl, Si-O-C, Si-N-Si, Si-O-Si structure or cyclic structure includes：

Organic silicon monomer containing double bond structure：Allyltrimethoxysilanis, vinyltriethoxysilane, vinyl trimethyl Silane, 3- cyclobutenyls trimethyl silane, vinyl tributyl ketoximyl silane, tetramethyl divinyl disiloxane, 1,2,2- tri- Fluoride-based tri-phenyl-silane；

The organic silicon monomer of the key containing Si-Cl：Tri-phenyl chloride, methylvinyldichlorosilane, trifluoro propyl trichlorosilane, three Fluoropropyl dimethyl dichlorosilane (DMCS), 3,5-dimethylphenyl chlorosilane, tributyl chlorosilane, benzyl dimethyl chlorosilane；

The organic silicon monomer of the structure containing Si-O-C：Tetramethoxy-silicane, trimethoxy hydrogen siloxane, n-octyl triethoxysilicane Alkane, phenyl triethoxysilane, vinyl three (2- methoxy ethoxies) silane, triethylvinylsilane silane, Hexaethyl ring three Siloxanes, 3- (methacryloxypropyl) propyl trimethoxy silicane, phenyl three (trimethylsiloxane group) silane, diphenyl diethyl Oxysilane, dodecyltrimethoxysilane, n-octytriethoxysilane, dimethoxysilane, 3- chloropropyl trimethoxies Base silane；

The organic silicon monomer of the structure containing Si-N-Si or Si-O-Si：Hexamethyldisilane base amine, three silane amino of pregnancy basic ring, six Methyl disilazane, hexamethyldisiloxane；

Organic silicon monomer containing cyclic structure：Hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, three silica of hexaphenyl ring Alkane, decamethylcyclopentaandoxane, octaphenylcyclotetrasiloxane, triphenyl silicol, Diphenylsilanediol, chromic acid are double (trityl silylation) ester, trifluoro propyl methyl cyclotrisiloxane, four silicon of 2,2,4,4- tetramethyl -6,6,8,8- tetraphenyls ring Oxygen alkane, t etram-ethyltetravinylcyclotetrasiloxane, 3- glycidyl ether oxypropyltriethoxysilanes, γ-glycidol ether Oxygen propyl trimethoxy silicane；

(3) surface hard is handled：

It is passed through oxygen and/or vapor, flow is 10~100 μ L/min, and plasma discharge power is 50-100W, type discharge The electric time is 60s-180s, and hard processing is carried out to the high insulating nano coating surface of composite construction；

(4) it post-processes：

Stopping is passed through oxygen and/or vapor, is simultaneously stopped plasma discharge, persistently vacuumizes, and keeps reaction chamber vacuum Degree is 10~200 millitorrs, is passed through air to an atmospheric pressure after 1~5min, stops the movement of base material, then take out base material i.e. It can；

Alternatively, stop be passed through oxygen and/or vapor, be simultaneously stopped plasma discharge, be filled with into reaction chamber air or Then inert gas is evacuated to 10-200 millitorrs to pressure 2000-5000 millitorrs, carry out above-mentioned inflation and vacuum step extremely It is few primary, air is passed through to an atmospheric pressure, is stopped the movement of base material, is then taken out base material.

2. a kind of preparation method of the high insulating rigid nano protecting coating of composite construction according to claim 1, feature It is：Base material generates movement in reaction chamber in the step (1), and substrate transport form carries out for base material relative response chamber Straight reciprocating motion or curvilinear motion, the curvilinear motion include circular motion, ellipse circular motion, planetary motion, spheric motion Or the curvilinear motion of other irregular routes.

3. a kind of preparation method of the high insulating rigid nano protecting coating of composite construction according to claim 1, feature It is：Base material is solid material in the step (1), the solid material be electronic product, electric component, Electronic Assemblies half at Product, pcb board, metallic plate, polytetrafluoroethylene (PTFE) plank or electronic component, and the substrate surface prepares organic silicon nano coating Its any interface can be exposed to water environment, mould environment, acid, basic solvent environment, acid, alkaline salt mist environment, acidic atmosphere afterwards Environment, organic solvent impregnate environment, cosmetics environment, and sweat environment makes in cold cycling shock environment or damp and hot alternation environment With.

4. a kind of preparation method of the high insulating rigid nano protecting coating of composite construction according to claim 1, feature It is：Reaction chamber is rotator shaped chamber or cube shaped chamber in the step (1), and volume is 50~1000L, instead The temperature of chamber is answered to control at 30~60 DEG C, it is 5~300sccm that the inert gas, which is passed through flow,.

5. a kind of preparation method of the high insulating rigid nano protecting coating of composite construction according to claim 1, feature It is：In the step (2)：It is passed through monomer A steam or monomer B steam, plasma discharge carries out chemical vapor deposition, sinks Plasma discharge processes include small-power continuous discharge, pulsed discharge or period alternating discharge during product.

6. a kind of preparation method of the high insulating rigid nano protecting coating of composite construction according to claim 5, feature It is：The deposition process plasma discharge process is small-power continuous discharge, specifically includes following deposition process at least Once：

Deposition process includes pretreatment stage and plating mem stage, and pretreatment stage plasma discharge power is 150~600W, is held Continuous 60~450s of discharge time, subsequently into plating mem stage, adjustment plasma discharge power is 10~150W, when continuous discharge Between 600~3600s.

7. a kind of preparation method of the high insulating rigid nano protecting coating of composite construction according to claim 5, feature It is：The deposition process plasma discharge process is pulsed discharge, specifically includes following deposition process at least once：

Deposition process includes pretreatment stage and plating mem stage, and pretreatment stage plasma discharge power is 150~600W, is held Continuous 60~450s of discharge time, subsequently into plating mem stage, plating mem stage is pulsed discharge, 10~300W of power, time 600s The frequency of~3600s, pulsed discharge are 1~1000HZ, and the duty ratio of pulse is 1:1~1:500.

8. a kind of preparation method of the high insulating rigid nano protecting coating of composite construction according to claim 5, feature It is：The deposition process plasma discharge process is period alternating discharge, specifically includes following deposition process at least one It is secondary：

Deposition process includes pretreatment stage and plating mem stage, and pretreatment stage plasma discharge power is 150~600W, is held Continuous 60~450s of discharge time, subsequently into plating mem stage, plated film phase plasma is period alternately variation electric discharge output, work( 10~300W of rate, time 600s~3600s, alternative frequency 1-1000Hz, plasma period alternately change electric discharge output wave Shape is zig-zag, sinusoidal waveform, square-wave waveform, current waveform in full-wave rectifier or half wave rectification wave.

9. a kind of preparation method of the high insulating rigid nano protecting coating of composite construction according to claim 1, feature It is：In the step (2), plasma discharge manner is radio frequency discharge, microwave discharge, intermediate frequency electric discharge, high-frequency discharge, electrical fire The waveform of flower electric discharge, the high-frequency discharge and intermediate frequency electric discharge is sinusoidal or bipolar pulse.