CN107587119A

CN107587119A - A kind of preparation method of the high insulating rigid nano protecting coating of composite construction

Info

Publication number: CN107587119A
Application number: CN201710729416.0A
Authority: CN
Inventors: 宗坚
Original assignee: WUXI RJ INDUSTRIES Co Ltd
Current assignee: Jiangsu Favored Nanotechnology Co Ltd
Priority date: 2017-08-23
Filing date: 2017-08-23
Publication date: 2018-01-16
Anticipated expiration: 2037-08-23
Also published as: CN107587119B; 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 inert gas is passed through, base material is produced motion, filter 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, the coating of the invention coating more existing than Parylene etc. under same thickness has more excellent barrier propterty, insulating properties and wearability.Solve at present using the problems such as coating abrasion performance existing for coating such as Parylene is insufficient, thickness is too thick, low production efficiency, hardening processing, add complex abrasion-proof silicon dioxide structure in coating, effectively increase 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 field, and in particular to 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 failed due to short circuit.Further, since in life Many electronic products easily touched and scraped in use, cause it destroyed.Therefore, for applied to electronics The protective coating of industry, except with excellent " three proofings " performance, it is necessary to have good insulating properties and preferable wearability.

At present, electronic product is protected using protective coating, is the effective ways for improving electronic product service life. Obtaining protective coating generally has two methods, liquid phase method and vapor phase method.Liquid phase method generally use three-proofing coating, electronic product is carried out After coating, using heat cure or photocuring, one layer of fine and close organic coating is formed on circuit boards, for protection circuit plate and its phase Close erosion of the equipment from environment.Three-proofing coating has good high and low temperature resistance；Into layer of transparent diaphragm, tool after its solidification Have it is superior insulate, be moistureproof, be anticreep, be shockproof, be dust-proof, anticorrosion, anti-aging, the performance such as Inverter fed motor.But liquid phase process can produce Raw waste water, waste gas and waste liquid, the solvent used can produce certain damage in itself to electronic device substrate, and its thickness is mostly in addition Tens microns, it is difficult to which control has necessarily in Nano grade, the electronic device function of being transmitted with signal that radiated for some needs Influence.

Gas phase rule includes the methods of evaporation, plasma gas phase deposition.Most typical evaporation coating is parylene coating, Developed and widely applied among electronic product protection by U.S. Union Carbide Co..Parylene coating is one kind to two The polymer of toluene, paraxylene is first heated to 680 degrees Celsius, 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 Measure 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 protection against the tide, waterproof, antirust, antiacid caustic corrosion.This Parylene is to deposit under vacuum conditions Produce, 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 that printed circuit board assembly gathers the main reason for influenceing Parylene vapour deposition conformal coat protection failure In 3~7 micron thickness local corrosion failure easily occurs for compound film coating, and thickness is applied in the case of high-frequency dielectric loss is not influenceed Degree should be >=30 microns.And the problems such as thick coating is easily caused weak heat-dissipating, signal obstructs, holiday increases.In addition, parylene coating The pre-processing requirements of the printed substrate protected for needs 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 preparing raw material cost is high, 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 It is low, usually less than H, under the conditions of meeting touch and scraping, easily scratched by external force and cause barrier propterty to be destroyed.

For problem above, a kind of environmental protection, good insulating, high rigidity are developed, and with excellent under coating thinner case The coating and preparation method of barrier propterty, there is important application value.

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

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

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

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

(4) it may be made as homogeneous film in the substrate surface of concavo-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 as micron-sized coating but also can prepare ultra-thin nanoscale Coating.

(7) designability of coating is strong, under plasma conditions, most Orqanics Monomers can be activated for The free radical of greater activity, and form coating on electronic product surface.To monomer dipole moment, chemical inertness, free volume sieve 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 composition 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.

At present, most of plasma coatings are traditional hydrocarbon oxygen organic compound, compared to these traditional organic coatings, Organic silicon coating has the characteristics that the feature of environmental protection, hardness are high, wearability is good, good insulating, in 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, make 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 Into colloidal sol, sol coating, finally by heat cure, one layer of dense coating is formed on model machine surface on processed exemplar.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) water or organic matter is needed to use to have a negative impact as solvent, these solvents to electronic product；

(2) waste water, waste liquid and waste gas be present, it is necessary to be 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, easily causes to damage under the conditions of touch and scraping, reduces service life.

The content of the invention

The present invention provides a kind of preparation of the high insulating rigid nano protecting coating of composite construction for solution above-mentioned technical problem Method.In the preparation process, filter 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.

Because plasma chemical vapor deposition process may be not only suitable for various of monomer, and to the composition of the coating of formation with The controllability of structure is strong, therefore, by the design of monomer and the optimization of technological parameter, coating composition and structure are carried out regulation and control with Construct, low dipole moment monomer and hard organosilicon monomer can be organically combined, formed has high-insulativity and high rigidity simultaneously Coating.This coating, under same thickness coating more existing than Parylene etc. have more excellent barrier propterty, insulating properties and Wearability.So as to effectively solve to use the problems existing for coating such as Parylene at present, such as coating abrasion performance deficiency, thickness too 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：Comprise the following steps：

(1) pre-treatment：

Base material is placed in the reaction chamber of nano coating Preparation equipment, reaction chamber continuously vacuumized, by reaction chamber Indoor vacuum 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 produce motion in reaction chamber；

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

Monomer A steam is passed through in reaction chamber, is 30~300 millitorrs to vacuum, opens plasma discharge, carry out Chemical vapor deposition, high insulating nano coating is prepared in substrate surface chemical vapor deposition, stopping is passed through monomer A steam, is passed through Monomer B steam, continue plasma discharge, carry out chemical vapor deposition, prepare 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 Compound, polyfunctionality unsaturated hydrocarbons and mass fraction shared by hydrocarbon derivative are 15~65% in the monomer A steam；

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 that monomer is atomized by charge pump, is volatilized and by the milli of low pressure 10~200 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：

Oxygen and/or vapor are passed through, 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) post-process：

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

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

Under low vacuum plasma discharge environment, by effective output to energy, make 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 With reference to polymerization forms nano thin-film, finally forms high-insulativity protective coating in substrate surface.

Base material produces motion in reaction chamber in the step (1), and substrate transport form is base material relative response chamber Straight reciprocating motion or curvilinear motion are carried out, the curvilinear motion includes circular motion, ellipse circular motion, planetary motion, sphere Motion 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) sheet material or electronic component, and the substrate surface prepares organic silicon nano Its any interface can be exposed to water environment, mould environment, acid, basic solvent environment, sour, alkaline salt mist environment, acidity after coating Atmospheric environment, organic solvent immersion environment, cosmetics environment, sweat environment, cold cycling shock environment or damp and hot alternation environment Middle use.

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

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

The deposition process plasma discharge process is small-power continuous discharge, specifically includes following deposition process extremely Less 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, 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 is pulsed discharge, 10~300W of power, when Between 600s~3600s, the frequency of pulsed discharge is 1~1000HZ, and the dutycycle of pulse is 1:1~1:500.

The deposition process plasma discharge process is cycle 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 cycle alternately change electric discharge Output, 10~300W of power, time 600s~3600s, alternative frequency 1-1000Hz, the alternately change electric discharge of plasma cycle 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：It is paraxylene, benzene, toluene, carbon tetrafluoride, α-methylstyrene, poly- To dichlorotoleune, dimethyl siloxane, molecular weight 500-50000 dimethyl silicone polymer, phenyl allyloxy, decafluorobiphenyl, ten fluorine Biphenyl ketone, perfluorinated allyl base benzene, tetrafluoroethene, hexafluoropropene, 1H, 1H- perfluoro capryls amine, perfluor dodecyl iodides, perfluor three Butylamine, the iodo PFOs of 1,8- bis-, 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 ethene, perfluor Dodecyl ethyl iodide, dibromo paraxylene, 1,1,4,4- tetraphenyl -1,3- butadiene；

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

Organic silicon monomer containing double bond structure：Allyltrimethoxysilanis, VTES, 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 TMOS；

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

Organic silicon monomer containing cyclic structure：Hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, the silicon of hexaphenyl ring three Oxygen alkane, decamethylcyclopentaandoxane, octaphenylcyclotetrasiloxane, triphenyl silicol, Diphenylsilanediol, chromic acid are double (trityl silylation) ester, trifluoro propyl methyl cyclotrisiloxane, the silicon of 2,2,4,4- tetramethyl -6,6,8,8- tetraphenyls ring four Oxygen alkane, t etram-ethyltetravinylcyclotetrasiloxane, 3- glycydoxies triethoxysilane, 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 is discharged, 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 Discharge and caused plasma electromagnetic field of high frequency.Microwave method is the energy excitation plasma using microwave, has energy profit The advantages of with efficiency high, 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 produces motion, improves coating deposition efficiency, and improve uniformity and the cause of coating layer thickness Close property.

Prepared coating is acidproof with insulation, waterproof and dampproof, mould proof, acid and alkali resistance solvent, acid and alkali resistance salt fog Property air, organic solvent-resistant immersion, 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 possessing above-mentioned barrier propterty, coating layer thickness is in the case of 1~1000nm, to frequency The influence of radio frequency communication signal of the rate in the range of 10M~8G is less than 5%.

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

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

2nd, base material moves in reaction chamber, the base material coating film thickness of diverse location is tended to consistent, solve by In different zones monomer density difference causes substrate surface coating layer thickness uneven in reaction chamber the problem of.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%, so as to reduce the row of tail gas exhaust Put, it is more green, it is significant in actual production efficiency is improved.

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

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

(2) because benzene ring structure and fluorine carbon structure have higher chemical inertness, its 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 Long difference, the difference of vapourizing temperature, give the Significant Change of the corresponding energy output of equipment and technological parameter, obtain it is compound, The polymer nanocomposite coating of grading structure, as parylene layer and hard organosilicon layer are compound, the exhausted of film was both ensure that Edge, the environmental corrosion resisting and abrasion resistance properties of the products such as electronic product are improved again.

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

4th, 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 enter One step improves compactness, wearability and the corrosion resistance of coating.

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, because the functional group being connected with silicon all has Higher reactivity, therefore, these organic silicon monomers have more cross-linking avtive spots；

Because hydrolysis easily occurs for the functional group that is connected in organic silicon monomer with silicon or alcoholysis, obtained structure are very easy to Generation condensation reaction, and be cross-linked with each other, each silicon atom provides at 1-4 avtive spot, has higher activity, therefore, Generation free radical is easier in the case of low-temperature plasma and cross-linking reaction occurs, forms the cross-linking compounds of densification, is improved 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 produces waste water, waste liquid, waste gas is it also avoid simultaneously.

5th, 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 substitutes the carbon on silicon atom completely, organosilicon can be oxidized to nano silicon.Water is introduced in monomer Steam, then hydrolysis can occur with organosilicon, produce nano silicon.Obtained nano silicon mass percent is about For 5%-20%；Because silica is atomic crystal, hardness is up to 1500Hv, and it is dispersed among coating, because disperse is strong Change effect, be 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 brings up to, when silica quality percentage in coating For 20%, coating hardness brings up 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, electronic equipment short circuit and open circuit etc. can be caused to damage.The film plating process of patent of the present invention increases Nanometer has been added to be significant in actual production efficiency is improved.Service life of the coating in corrosive atmosphere is improved, Improve the protecting effect of product.It is mainly used in following product：

(1), portable equipment keyboard：Portable keyboard has the characteristics of small and light, is usually used in the equipment such as computer, mobile phone. It can be easy to user to be handled official business in route.But when it runs into 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 easily short-circuit, and then damage.After carrying out plated film to it using such nano coating, when can Surface of keyboard easy to clean is ensured, function is intact after meeting water so that keyboard can adapt to more acute environment.

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

(3), intelligent fingerprint lock：Fingerprint Lock is intelligent lock, and 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, its inner wire Louis is short Road, it is difficult to repair, it is necessary to lock is torn in violence open, after the coating, this problem can be avoided.

(4), audiphone, bluetooth earphone：Audiphone does not have connection, after the coating, Yong Huke with bluetooth earphone To be used within a certain period of time under water environment, such as have a bath, on rainy day, equipment will not infiltrate because of rainwater to be damaged.

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

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

(7), other equipment for needing waterproof：Including needing the operation in wet environment, or it is likely encountered common liquid The fortuitous event such as splash, the equipment of internal light current circuit normal operation can be influenceed.

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, audiphone.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 plant equipment And pipeline：Flue desulfurization equipment, seal (acid/base lubricating oil), pipeline, valve, Large Diameter Pipeline sea conveyance conduit liner etc. Place.4 various reactors, 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 Aero-Space, 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 soaks, 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 Thing, nitrogen-containing 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 Car electrical equipment, such as aviation, automobile, household electrical appliances, the equipment in scientific research field.

Embodiment

The present invention is described in detail with reference to specific embodiment, but the invention is not limited in specific embodiment.

Embodiment 1

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

(1) pre-treatment：

Base material is placed in the reaction chamber of nano coating Preparation equipment, closed reaction chamber is simultaneously continuously taken out to reaction chamber Vacuum, the vacuum in reaction chamber is extracted into 10 millitorrs, is passed through inert gas Ar, opening movement mechanism, is reacting base material Motion is produced in chamber；

Base material is solid material in step (1), and the solid material is block 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 produces motion in reaction chamber in step (1), and substrate transport form is carried 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：

Monomer A steam is passed through in reaction chamber, is 30 millitorrs to vacuum, opens plasma discharge, carry out chemistry Vapour deposition, high insulating nano coating is prepared in substrate surface chemical vapor deposition, stopping is passed through monomer A steam, is passed through monomer B Steam, continue plasma discharge, carry out chemical vapor deposition, 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 low dipole moment Orqanics Monomer and the mixture of three kinds of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative, it is described Polyfunctionality unsaturated hydrocarbons and the mass fraction shared by hydrocarbon derivative are 15% in monomer A steam；

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, the propylene of tripropylene glycol two Acid esters, 1,6- hexanediyl esters,

The monomer B vapor compositions include：

Three kinds of organic silicon monomers and the mixture of a kind of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative containing double bond structure, Polyfunctionality unsaturated hydrocarbons and the mass fraction shared by hydrocarbon derivative are 65% in the monomer B steam；

Three kinds of organic silicon monomers containing double bond structure are：VTES, 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,

Monomer A and monomer B steam are passed through to be atomized, being volatilized by charge pump by monomer and introduced by the millitorr of low pressure 10 Reaction chamber, the flow for being passed through monomer A and monomer B is 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, specifically includes following deposition process once：

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：

Oxygen is passed through, 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) post-process：

Stopping is passed through oxygen, while stops plasma discharge, persistently vacuumizes, and it is 10 millis to keep reaction chamber vacuum Hold in the palm, be passed through air to an atmospheric pressure after 1min, then take out base material.

The coating dielectric constant that said process obtains is 2.73, hardness 2H, aluminum material and pcb board after plated film, cold, Thermal cycle impact test effect is as follows：

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 Vacuumize, the vacuum in reaction chamber is extracted into 30 millitorrs, be passed through inert gas He, start motion, carry out base material Motion；

Base material is solid material in step (1), and the solid material is block 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：

Monomer A steam is passed through in reaction chamber, is 70 millitorrs to vacuum, opens plasma discharge, carry out chemistry Vapour deposition, high insulating nano coating is prepared in substrate surface chemical vapor deposition, stopping is passed through monomer A steam, is passed through monomer B Steam, continue plasma discharge, carry out chemical vapor deposition, 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：

Five kinds of low dipole moment Orqanics Monomers and the mixture of a kind of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative, it is described Polyfunctionality unsaturated hydrocarbons and the mass fraction shared by hydrocarbon derivative are 65% in monomer A steam；

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 of the structure containing Si-Cl and three kinds of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative Thing, polyfunctionality unsaturated hydrocarbons and mass fraction shared by hydrocarbon derivative are 15% in the monomer B steam；

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,

Monomer A and monomer B steam are passed through to be atomized, being volatilized by charge pump by monomer and introduced by the millitorr of low pressure 30 Reaction chamber, the flow for being passed through monomer A and monomer B is 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) post-process：

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

The coating dielectric constant that said 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 Vacuumize, the vacuum in reaction chamber is extracted into 80 millitorrs, be passed through inert gas Ar and He mixed gas, start fitness machine Structure, moved base material；

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

Monomer A steam is passed through in reaction chamber, is 120 millitorrs to vacuum, opens plasma discharge, carry out chemistry Vapour deposition, high insulating nano coating is prepared in substrate surface chemical vapor deposition, stopping is passed through monomer A steam, is passed through monomer B Steam, continue plasma discharge, carry out chemical vapor deposition, 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：

Four kinds of low dipole moment Orqanics Monomers and the mixture of three kinds of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative, it is described Polyfunctionality unsaturated hydrocarbons and the mass fraction shared by hydrocarbon derivative are 57% in monomer A steam；

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 Thing, polyfunctionality unsaturated hydrocarbons and mass fraction shared by hydrocarbon derivative are 55% in the monomer B steam；

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,

Monomer A and monomer B steam are passed through to be atomized, being volatilized by charge pump by monomer and introduced by the millitorr of low pressure 80 Reaction chamber, the flow for being passed through monomer A and monomer B is 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, specifically includes following deposition process once：

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 dutycycle of pulse is 1:500；

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

(3) surface hard is handled：

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

(4) post-process：

Stopping is passed through oxygen and vapor, while stops plasma discharge, persistently vacuumizes, and keeps reaction chamber vacuum Spend for 100 millitorrs, be passed through air to an atmospheric pressure after 3min, then take out base material.

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

Prepare waterproof electrical breakdown withstand coating electric component and underwater soaking experimental result is tested under different voltages：

The classification of waterproof of IPX 7 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 Vacuumize, the vacuum in reaction chamber is extracted into 100 millitorrs, be passed through inert gas Ar, start motion, carry out base material Motion；

The volume of reaction chamber is 780L in step (1), and the temperature control of reaction chamber is passed through inert gas at 53 DEG C 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：

Monomer A steam is passed through in reaction chamber, is 180 millitorrs to vacuum, opens plasma discharge, carry out chemistry Vapour deposition, high insulating nano coating is prepared in substrate surface chemical vapor deposition, stopping is passed through monomer A steam, is passed through monomer B Steam, continue plasma discharge, carry out chemical vapor deposition, 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：

Six kinds of low dipole moment Orqanics Monomers and the mixture of four kinds of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative, it is described Polyfunctionality unsaturated hydrocarbons and the mass fraction shared by hydrocarbon derivative are 42% in monomer A steam；

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 organic silicon monomer and the mixture of 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：Chromic acid double (trityl silylation) ester, 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,

Monomer A and monomer B steam are passed through to be atomized monomer by charge pump, volatilizing and being drawn by the millitorr of low pressure 100 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 dutycycle 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：

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

(4) post-process：

Stopping is passed through oxygen and vapor, while stops plasma discharge, persistently vacuumizes, and keeps reaction chamber vacuum Spend for 200 millitorrs, be passed through compressed air to an atmospheric pressure after 4min, then take out base material.

The coating dielectric constant that said 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 Vacuumize, the vacuum in reaction chamber is extracted into 200 millitorrs, be passed through inert gas Ar and He mixed gas, start motion Mechanism, moved base material；

Base material is solid material in step (1), and the solid material is block 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 control of reaction chamber is passed through inert gas at 60 DEG C 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：

Monomer A steam is passed through in reaction chamber, is 300 millitorrs to vacuum, opens plasma discharge, carry out chemistry Vapour deposition, high insulating nano coating is prepared in substrate surface chemical vapor deposition, stopping is passed through monomer A steam, is passed through monomer B Steam, continue plasma discharge, carry out chemical vapor deposition, 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：

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

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, polyfunctionality unsaturated hydrocarbons and mass fraction shared by hydrocarbon derivative are 23% in the monomer B steam；

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

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

Monomer A and monomer B steam are passed through to be atomized monomer by charge pump, volatilizing and being drawn by the millitorr of low pressure 200 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 cycle alternating discharge, specifically includes following deposition process once：

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 alternately to change electric discharge output, power in the cycle 10W, time 3600s, alternative frequency 1Hz, the plasma cycle, alternately change 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) post-process：

Stopping is passed through oxygen, while stops plasma discharge, and inert gas is filled with into reaction chamber to pressure 2000 Millitorr, 10 millitorrs are then evacuated to, carry out above-mentioned inflation and vacuum step once, be passed through air to an atmospheric pressure, stop The only motion of base material, then takes out base material.

Said process obtains the aluminum material after coating and plated film, hardness 4H, it is as follows to test effect：

(2) organic solvent-resistant test result：(contact angle change is less than 5 ° after pass represents immersion a period of time)

(3) sour, alkaline test result：(after representing 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 Vacuumize, the vacuum in reaction chamber is extracted into 140 millitorrs, be passed through inert gas Ar, start motion, carry out base material Motion；

Step (1) base material is solid material, and the solid material is block 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 control of reaction chamber is passed through inert gas at 47 DEG C Flow is 150sccm.

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

Monomer A steam is passed through in reaction chamber, is 220 millitorrs to vacuum, opens plasma discharge, carry out chemistry Vapour deposition, high insulating nano coating is prepared in substrate surface chemical vapor deposition, stopping is passed through monomer A steam, is passed through monomer B Steam, continue plasma discharge, carry out chemical vapor deposition, 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：

Seven kinds of low dipole moment Orqanics Monomers and the mixture of three kinds of polyfunctionality unsaturated hydrocarbons and hydrocarbon derivative, it is described Polyfunctionality unsaturated hydrocarbons and the mass fraction shared by hydrocarbon derivative are 23% in monomer A steam；

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 Thing, polyfunctionality unsaturated hydrocarbons and mass fraction shared by hydrocarbon derivative are 38% in the monomer B steam；

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,

Monomer A and monomer B steam are passed through to be atomized monomer by charge pump, volatilizing and being drawn by the millitorr of low pressure 140 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 cycle 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 alternately to change electric discharge output, power in the cycle 300W, time 600s, alternative frequency 1000Hz, the plasma cycle, alternately change electric discharge output waveform was halfwave rectifier ripple 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) post-process：

Stopping is passed through vapor, while stops plasma discharge, and air is filled with into reaction chamber to the milli of pressure 5000 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 motion 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：(contact angle change is less than 5 ° after pass represents immersion a period of time)

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

Claims

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

(1) pre-treatment：

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

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

Monomer A steam is passed through in reaction chamber, is 30~300 millitorrs to vacuum, opens plasma discharge, carry out chemistry Vapour deposition, high insulating nano coating is prepared in substrate surface chemical vapor deposition, stopping is passed through monomer A steam, is passed through monomer B Steam, continue plasma discharge, carry out chemical vapor deposition, 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：

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

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 A kind of few mixture of 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；

(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) post-process：

Stopping is passed through oxygen and/or vapor, while stops plasma discharge, persistently vacuumizes, and keeps reaction chamber vacuum Spend for 10~200 millitorrs, be passed through air to an atmospheric pressure after 1~5min, stop the motion of base material, then take out base material i.e. Can；

Or stop being passed through oxygen and/or vapor, while stop plasma discharge, be filled with into reaction chamber air or Then inert gas is evacuated to 10-200 millitorrs, carries out above-mentioned inflation and vacuum step extremely to pressure 2000-5000 millitorrs Less once, air is passed through to an atmospheric pressure, stops the motion of base material, then takes out base material.
2. a kind of preparation method of the high insulating rigid nano protecting coating of composite construction according to claim 1, its feature It is：Base material produces motion in reaction chamber in the step (1), and substrate transport form is carried 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, its feature It is：Base material is solid material in the step (1), the solid material be electronic product, electric component, Electronic Assemblies half into Product, pcb board, metallic plate, polytetrafluoroethylene (PTFE) sheet material 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, sour, alkaline salt mist environment, acidic atmosphere afterwards Environment, organic solvent immersion environment, cosmetics environment, 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, its feature It is：Reaction chamber is rotator shaped chamber or cube shaped chamber in the step (1), and its volume is 50~1000L, instead Answering the temperature control of chamber, it is 5~300sccm that the inert gas, which is passed through flow, at 30~60 DEG C.
5. a kind of preparation method of the high insulating rigid nano protecting coating of composite construction according to claim 1, its feature It is：In the step (2)：Monomer A steam or monomer B steam are passed through, plasma discharge, carries out chemical vapor deposition, is sunk Plasma discharge processes include small-power continuous discharge, pulsed discharge or cycle 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, its 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, during 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, its 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 ~3600s, the frequency of pulsed discharge is 1~1000HZ, and the dutycycle 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, its feature It is：The deposition process plasma discharge process is cycle 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 alternately to change electric discharge output, work(in the cycle 10~300W of rate, time 600s~3600s, alternative frequency 1-1000Hz, plasma cycle 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, its feature It is：

The low dipole moment Orqanics Monomer includes：It is paraxylene, benzene, toluene, carbon tetrafluoride, α-methylstyrene, poly- to two Chlorotoluene, dimethyl siloxane, molecular weight 500-50000 dimethyl silicone polymer, phenyl allyloxy, decafluorobiphenyl, decafluorobiphenyl Ketone, perfluorinated allyl base benzene, tetrafluoroethene, hexafluoropropene, 1H, 1H- perfluoro capryls amine, perfluor dodecyl iodides, perfluorotributylamine, The iodo PFOs of 1,8- bis-, 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) ethylmethyl acrylate, 2- (perfluoro capryl) ethylmethyl acrylate, 2- (perfluoro capryl) iodic ether, perfluoro decyl ethyl iodide, 1,1,2,2- tetrahydrochysenes are complete Fluorine hexyl iodide, perfluorobutyl ethylene, 1H, 1H, 2H- perfluor -1- decene, 2,4,6- tri- (perfluor heptyl) -1,3,5- triazines, perfluor Hexyl ethene, 3- (n-perfluoro-octyl) -1,2 epoxy prapane, perfluoro-cyclicether, perfluorododecyl ethene, perfluorododecyl second Base iodine, dibromo paraxylene, 1,1,4,4- tetraphenyl -1,3- butadiene；

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, VTES, 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 TMOS, 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, the silane amino of pregnancy basic ring three, six Methyl disilazane, hexamethyldisiloxane；

Organic silicon monomer containing cyclic structure：Hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, the silica of hexaphenyl ring three Alkane, decamethylcyclopentaandoxane, octaphenylcyclotetrasiloxane, triphenyl silicol, Diphenylsilanediol, chromic acid are double (trityl silylation) ester, trifluoro propyl methyl cyclotrisiloxane, the silicon of 2,2,4,4- tetramethyl -6,6,8,8- tetraphenyls ring four Oxygen alkane, t etram-ethyltetravinylcyclotetrasiloxane, 3- glycydoxies triethoxysilane, 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 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.
10. a kind of preparation method of the high insulating rigid nano protecting coating of composite construction according to claim 1, its feature It is：In the step (2), plasma discharge manner is radio frequency discharge, microwave discharge, intermediate frequency electric discharge, high-frequency discharge, electricity fire The waveform of flower electric discharge, the high-frequency discharge and intermediate frequency electric discharge is sinusoidal or bipolar pulse.