WO2019037443A1 - Procédé de préparation d'un revêtement nano-protecteur dur d'organosilicium - Google Patents

Procédé de préparation d'un revêtement nano-protecteur dur d'organosilicium Download PDF

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WO2019037443A1
WO2019037443A1 PCT/CN2018/082832 CN2018082832W WO2019037443A1 WO 2019037443 A1 WO2019037443 A1 WO 2019037443A1 CN 2018082832 W CN2018082832 W CN 2018082832W WO 2019037443 A1 WO2019037443 A1 WO 2019037443A1
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discharge
coating
silicone
monomer
reaction chamber
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PCT/CN2018/082832
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Chinese (zh)
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宗坚
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江苏菲沃泰纳米科技有限公司
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Publication of WO2019037443A1 publication Critical patent/WO2019037443A1/fr
Priority to US16/798,097 priority Critical patent/US11185883B2/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/513—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using plasma jets
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment

Definitions

  • the invention belongs to the technical field of plasma chemical vapor deposition, and in particular relates to a preparation method of a silicone nano protective coating.
  • Anti-mold, anti-moist and anti-salt spray (referred to as three-proof) is an important problem that needs to be solved in the process of storage, transportation and use of electronic devices. Mold, salt spray and moisture often cause electronic devices to fail due to short circuits. Therefore, applying a protective coating on the surface of electronic products is an important method to improve the service life of electronic products. As the variety of electronic products continues to increase, more and more electronic devices need to be touched and operated, so that the protective coating is damaged by external force, resulting in a decrease in coating protection performance. Therefore, in addition to the excellent "three-proof" performance, the protective coating applied to the electronics industry must have a certain strength, hardness and wear resistance.
  • the use of protective coatings to protect electronic products is an effective way to improve the service life of electronic products.
  • the liquid phase method usually adopts three anti-paints. After coating the electronic products, it uses thermal curing or photocuring to form a dense organic coating on the circuit board to protect the circuit boards and related equipment from environmental pollution. .
  • the three anti-paint has good resistance to high and low temperature; it forms a transparent protective film after curing, and has superior properties of insulation, moisture, leakage, shock, dust, corrosion, aging and corona resistance.
  • the liquid phase method will produce waste water, waste gas and waste liquid.
  • the solvent used will cause certain damage to the electronic device substrate itself.
  • the thickness is mostly several tens of micrometers, which is difficult to control at the nanometer level. For some electrons requiring heat dissipation and signal transmission. Device features will have an impact.
  • the gas phase method includes methods such as vapor deposition and plasma vapor deposition.
  • the most typical vapor deposition coating is a parylene coating, developed by Union Carbide Co. of the United States and widely used in electronic product protection.
  • the parylene coating is a p-xylene polymer that first heats para-xylene to 680 degrees Celsius to form an active para-xylene dimer. After the deposition chamber is lowered in temperature, the dimer is deposited in the electron. On the surface of the product, a polymer film is formed.
  • the parylene coating Since the paraxylene structure is highly symmetrical, the dipole moment is 0, and due to the presence of the benzene ring, the polymer molecule has a large free volume; and at the same time, due to the relatively large molecular weight of the polymer, the coating is dense. Due to the above characteristics, the parylene coating has low water, gas permeability and high barrier effect to achieve moisture, water, rust and acid and alkali corrosion resistance. This parylene is deposited under vacuum and can be used in applications where liquid coatings cannot be involved, such as high frequency circuits and very weak current systems. The thickness of the polymer film coating is the main reason for the protection failure of the para-xylene vapor-deposited conformal coating.
  • the polymer film coating of the printed circuit board component is prone to local rust failure at a thickness of 3 to 7 microns without affecting the high.
  • the coating thickness should be ⁇ 30 ⁇ m in the case of frequency dielectric loss.
  • Parylene coating requires high pretreatment of printed circuit boards that need protection, such as conductive components, signal transmission components, RF components, etc., in the vapor deposition of conformal coatings, it is necessary to pre-mask the circuit board components to avoid Affects component performance. This drawback has brought great limitations to the application of parylene coating.
  • Pyrene coatings have high cost of raw materials, harsh coating preparation conditions (high temperature, high vacuum requirements), low film formation rate, and thick coatings tend to cause poor heat dissipation, signal blocking, and increased coating defects.
  • the reactant monomers in this method can only select p-xylene and p-xylene chloride, and the coating structure and function are poorly controllable. Due to the above reasons, it is difficult to widely apply the parylene coating
  • Plasma chemical vapor deposition is a technique in which a reactive gas is activated by a plasma to promote a chemical reaction on a surface of a substrate or a near surface to form a solid film.
  • Plasma chemical vapor deposition coating has the following advantages
  • the plasma polymerization film is stable in chemical and physical properties such as solvent resistance, chemical corrosion resistance, heat resistance, and abrasion resistance.
  • the plasma polymerization film has good adhesion to the substrate.
  • a uniform film can also be formed on the surface of the substrate having irregular irregularities.
  • the coating preparation temperature is low, and can be carried out under normal temperature conditions, thereby effectively avoiding damage to temperature sensitive devices.
  • the plasma process can not only prepare a coating having a thickness of a micron order but also can prepare an ultra-thin nano-scale coating.
  • the coating is highly configurable. Under plasma conditions, most of the organic monomers can be activated into highly active free radicals and form a coating on the surface of the electronic product.
  • the screening and design of the monomer dipole moment, chemical inertness, and free volume is an important strategy for obtaining a coating with good insulation and excellent protection in a thin condition.
  • the coating structure is highly controllable, and the composition and proportion of the monomer can be changed at any time, so that the coating has a special structure such as multilayer, gradient and modulation.
  • the substrate In the preparation process of the existing plasma chemical vapor deposition coating, the substrate is fixed, and the motion state of the substrate is not related to the discharge energy of the plasma; the stationary substrate is treated by the continuous discharge method.
  • the activated chain scission in the monomer is generally formed into a film by simple stacking under the action of continuous discharge, and the obtained plating layer generally has a loose structure and even a high degree of pulverization, which is disadvantageous to the formation of a microscopic dense structure of the coating layer. Waterproof, moisture-proof, corrosion-resistant, solvent-resistant and other protective properties are poor.
  • the stationary substrate may cause slow deposition of coatings in some areas, low production efficiency, and a large difference in uniformity and compactness.
  • silicone coatings are environmentally friendly, have high hardness, good wear resistance, and good insulation properties. Industry applications are becoming more widespread.
  • the silicone monomer itself is non-toxic and does not decompose into toxic and harmful substances. After polymerization of the monomer, the polymer coating has high silicon due to silicon oxide bond or inorganic SiO 2 nanoparticles formed in the coating. Hardness, good insulation and heat resistance.
  • most silicone coatings are currently obtained by the liquid phase method.
  • the silicone monomer is hydrolyzed in solution to form a sol.
  • the sol is applied to the sample to be processed and finally thermally cured to form a dense coating on the surface of the sample.
  • the thickness of the coating is typically from a few microns to a few microns.
  • Liquid-phase silicone coating technology although more environmentally friendly than traditional liquid-phase coating technology, has many shortcomings:
  • organic coatings obtained by plasma deposition such as fluorocarbon coatings, parylene coatings, etc., usually have a hardness of HB-2H, which is easy to cause damage under touch and scratch conditions, reducing service life. .
  • the present invention provides a method for preparing a silicone hard nano protective coating to solve the above technical problems.
  • the substrate is kept in motion by the combination of the motion characteristics of the substrate and the plasma discharge energy, and the plasma discharge energy is output.
  • the plasma discharge generates a plasma, and by controlling the relationship between the plasma discharge energy and the bond energy of the monomer, the effective activation of the higher energy active group in the monomer component by the low temperature plasma is obtained, and at the same time,
  • the additional active sites introduced are cross-linked and polymerized in a plasma environment to form a dense network structure.
  • the present invention replaces a conventional hydrocarbon-hydrogen organic compound monomer with a silicone monomer. Since the functional group attached to the silicon in the silicone monomer is liable to undergo hydrolysis or alcoholysis, the obtained structure is very susceptible to condensation reaction and cross-linking with each other. Each silicon atom provides at least 1-4 active sites and has high activity. Therefore, in the case of low temperature plasma, free radicals are generated and cross-linking reaction occurs, forming a dense cross-linking compound and improving the protective property.
  • the plasma deposition method can achieve precise and controllable coating thickness from nanometer to micrometer, and does not require the use of solvents, and also avoids the shortage of wastewater, waste liquid, exhaust gas, etc. by the liquid phase silicone coating method.
  • the silicone can be oxidized to nano silica.
  • hydrolysis reaction with the silicone can be carried out to produce nano silica.
  • the obtained nano-silica has a mass percentage of about 5% to 20%; since the silica is an atomic crystal and has a hardness of up to 1500 Hv, it is dispersed in the coating layer, and the hardness of the coating can be greatly improved due to the dispersion strengthening effect.
  • the organic coating obtained by plasma deposition usually has a hardness of HB-2H. When the mass percentage of silica in the coating is 5%, the hardness of the coating can be increased to H-3H. When the mass percentage of silica in the coating is 20%, the coating hardness is increased to 2H-4H.
  • a method for preparing a silicone hard nano protective coating comprising: the following steps:
  • the substrate is placed in a reaction chamber of the nano-coating preparation device, and the reaction chamber is continuously evacuated, and the vacuum in the reaction chamber is pumped to 10 to 200 mTorr, and an inert gas of He, Ar or He and Ar is introduced. Mixing the gas, opening the moving mechanism to cause the substrate to move in the reaction chamber;
  • the monomer vapor component comprises:
  • the mass fraction of polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives in the monomer vapor is 15-65%;
  • the monomer steam is introduced into the reaction chamber by atomizing, volatilizing and introducing the monomer into the reaction chamber by a low pressure of 10 to 200 mTorr, and the flow rate of the monomer is 10 to 1000 ⁇ L/min;
  • the flow rate is 10 ⁇ 100 ⁇ L / min, wherein oxygen and water vapor can be mixed in any ratio, plasma discharge, discharge power is 50-100W, continuous discharge Hard time treatment of the surface of the silicone nano-coating layer for 60s-180s;
  • stopping the introduction of the oxygen and/or water vapor while stopping the plasma discharge charging the reaction chamber with air or an inert gas to a pressure of 2000-5000 mTorr, and then evacuating to 10-200 mTorr, The aeration and evacuation steps are performed at least once, the air is introduced to an atmospheric pressure, the movement of the substrate is stopped, and then the substrate is taken out.
  • the substrate generates motion in the reaction chamber, and the substrate moves in the form of a linear reciprocating motion or a curved motion of the substrate relative to the reaction chamber, the curved motion including circular motion, elliptical motion, planetary motion, Curved motion of spherical motion or other irregular routes.
  • the substrate in the step (1) is a solid material
  • the solid material is an electronic product, an electrical component, an electronic assembly semi-finished product, a PCB board, a metal plate, a polytetrafluoroethylene plate or an electronic component, and the surface of the substrate
  • any interface can be exposed to water environment, mold environment, acid, alkaline solvent environment, acid, alkaline salt spray environment, acidic atmospheric environment, organic solvent soaking environment, cosmetic environment, sweat environment, Use in cold or hot cycle impact environment or wet heat alternating environment.
  • the reaction chamber is a rotating body chamber or a cubic chamber
  • the volume of the reaction chamber is 50-1000 L
  • the temperature of the reaction chamber is controlled at 30-60 ° C
  • the inert gas is introduced into the flow. It is 5 to 300 sccm.
  • the plasma discharge process during the deposition process includes low power continuous discharge, pulse discharge or periodic alternating discharge.
  • the plasma discharge process during the deposition process is a low power continuous discharge, specifically including the following deposition process at least once:
  • the deposition process includes a pretreatment stage and a coating stage.
  • the plasma discharge power in the pretreatment stage is 150-600 W
  • the continuous discharge time is 60-450 s
  • the plasma discharge power is adjusted to 10 to 150 W
  • the continuous discharge time is 600 to 3600 s. .
  • the plasma discharge process during the deposition is a pulse discharge, specifically including the following deposition process at least once:
  • the deposition process includes a pretreatment stage and a coating stage.
  • the plasma discharge power of the pretreatment stage is 150-600 W, and the continuous discharge time is 60-450 s, and then enters the coating stage.
  • the coating stage is pulse discharge, the power is 10 to 300 W, and the time is 600 s to 3600 s.
  • the frequency of the pulse discharge is 1 to 1000 Hz, and the duty ratio of the pulse is 1:1 to 1:500.
  • the plasma discharge process during the deposition process is a periodic alternating discharge, specifically including the following deposition process at least once:
  • the deposition process includes a pretreatment stage and a coating stage.
  • the plasma discharge power in the pretreatment stage is 150-600 W, and the continuous discharge time is 60-450 s, and then enters the coating stage.
  • the plasma in the coating stage is a periodic alternating discharge output with a power of 10 to 300 W.
  • the time is 600s ⁇ 3600s, the frequency conversion rate is 1-1000Hz, and the plasma cycle alternately changes.
  • the discharge output waveform is a sawtooth waveform, a sinusoidal waveform, a square wave waveform, a full-wave rectified waveform or a half-wave rectified waveform.
  • the silicone monomer containing a double bond, a Si—Cl, a Si—O—C, a Si—N—Si, a Si—O—Si structure or a ring structure includes:
  • Silicone monomer containing double bond structure allyl trimethoxy silane, vinyl triethoxy silane, vinyl trimethyl silane, 3-butenyl trimethyl silane, vinyl tributyl ketone fluorenyl Silane, tetramethyldivinyldisiloxane, 1,2,2-trifluorovinyltriphenylsilane;
  • Silicone monomer containing Si-Cl bond triphenylchlorosilane, methylvinyldichlorosilane, trifluoropropyltrichlorosilane, trifluoropropylmethyldichlorosilane, dimethylphenylchlorosilane , tributylchlorosilane, benzyldimethylchlorosilane;
  • Silicone monomer containing Si-OC structure tetramethoxysilane, trimethoxyhydrogensiloxane, n-octyltriethoxysilane, phenyltriethoxysilane, vinyltris(2-methoxy Ethyl ethoxy) silane, triethyl vinyl silane, hexaethylcyclotrisiloxane, 3-(methacryloyloxy)propyl trimethoxy silane, phenyl tris(trimethyl siloxane group Silane, diphenyldiethoxysilane, dodecyltrimethoxysilane, n-octyltriethoxysilane, dimethoxysilane, 3-chloropropyltrimethoxysilane;
  • Silicone monomer containing Si-N-Si or Si-O-Si structure hexamethyldisilazide, hexamethylcyclotrisilylamino, hexamethyldisilazane, hexamethyldisiloxane;
  • Silicone monomer containing cyclic structure hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, hexaphenylcyclotrisiloxane, decamethylcyclopentasiloxane, octaphenyl ring Tetrasiloxane, triphenylhydroxysilane, diphenyldihydroxysilane, bis(tritylsilyl) chromate, trifluoropropylmethylcyclotrisiloxane, 2,2,4,4 -tetramethyl-6,6,8,8-tetraphenylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, 3-glycidoxypropyltriethoxysilane, ⁇ - glycidyloxypropyltrimethoxysilane;
  • the polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives include:
  • the plasma discharge mode is radio frequency discharge, microwave discharge, intermediate frequency discharge, high frequency discharge, and electric spark discharge
  • the waveforms of the high frequency discharge and the intermediate frequency discharge are sinusoidal or double A pole pulse
  • a radio frequency plasma is a plasma generated by discharge of a high frequency electromagnetic field.
  • the microwave method utilizes the energy of the microwave to excite the plasma, and has the advantages of high energy utilization efficiency.
  • the electrodeless discharge and the plasma are pure, it is an excellent method for high-quality, high-rate, large-area preparation.
  • the motion characteristics of the substrate and the plasma discharge energy are combined.
  • the substrate generates motion, improves the deposition efficiency of the coating, and improves the uniformity and compactness of the coating thickness.
  • the prepared coating has good wear resistance, and has waterproof and moisture proof, mold proof, acid resistance, alkaline solvent, acid and alkali salt spray, acid atmosphere, organic solvent immersion, cosmetics resistance, sweat resistance and resistance.
  • Thermal and thermal cycle impact (-40 ° C ⁇ +75 ° C), resistance to heat and humidity (humidity 75% ⁇ 95%) and other characteristics.
  • the coating thickness is between 1 and 1000 nm, and the influence on the RF communication signal in the range of 10M to 8G is less than 5%.
  • the plasma chemical vapor deposition method is more environmentally friendly than the liquid phase three-coating coating method; and the deposition temperature is lower, the speed is faster, and the coating structure and composition are controllable compared to the vapor deposition parylene method. Strong, the monomer is highly selective.
  • the substrate moves in the reaction chamber, so that the coating thickness of the substrate at different positions tends to be uniform, which solves the problem that the thickness of the coating on the surface of the substrate is not uniform due to the difference in monomer density in different regions of the reaction chamber.
  • the amount of chemical monomer raw materials used in monomer steam is only 10% to 15% of the amount in other prior art, thereby reducing emissions of exhaust gas, making it more environmentally friendly and improving actual production efficiency. It has great significance.
  • General plasma polymerization uses a monofunctional hydrocarbon-hydrogen organic compound monomer to obtain a coating having a certain cross-linking structure.
  • the crosslinked structure is formed by a plurality of active sites formed by chain scission of a monomer during plasma discharge by cross-linking.
  • this crosslinked structure is relatively loose, contains more linear components, and is resistant to solution penetration and solubility.
  • the silicon-bonded functional groups in the silicone monomer can undergo a condensation reaction with each other, and therefore, a three-dimensional network can occur between the monomer and the monomer.
  • Cross-linking can further improve the compactness, wear resistance and corrosion resistance of the coating.
  • An additional crosslinking point is introduced by introducing other monomer components having a polyfunctional crosslinked structure to form a crosslinked structure.
  • the active group with higher energy in the monomer component is broken to form an active point by effective control and output of energy, and the additional active point introduced is in the plasma environment. They cross-link and polymerize to form a dense network structure.
  • the mesh structure Compared with the loose coating composition with more linear components, the mesh structure has better compactness and can effectively improve the anti-wear and anti-corrosion properties of the film.
  • the surface of the coated substrate is activated to obtain a plurality of active sites.
  • the active sites are combined with the active radicals of the plasma-excited monomeric material with strong chemical bonds, and various forms of primitives are generated.
  • the reaction makes the nano film of the base material have excellent bonding force and mechanical strength.
  • the invention utilizes plasma chemical vapor deposition to obtain a protective coating with excellent performance by controlling the structure of the monomer and the coating.
  • the coating has the following advantages: the thickness is controllable between 20 nm and 10 ⁇ m; It is controllable between 2H-4H; it has excellent insulation performance and underwater power resistance; it has excellent three-proof performance.
  • the silicone-based coating can achieve a hardness of 2H-4H, which can effectively improve the wear resistance and prolong the service life of the coating. .
  • the corresponding energy output and effective changes of process parameters are given to the device, and the composite is obtained.
  • the gradual structure of the polymer nano-coating not only ensures the hydrophobicity of the film, but also improves the corrosion resistance and wear resistance of products such as electronic products.
  • the mass percentage of silica in the coating is 20%, the ratio is The abrasion resistance of the silica-free coating is increased by 2-3 times.
  • the typical plasma organic coating has a hardness of HB-2H, has poor wear resistance, and has a relatively short service life.
  • the coating method of the patent of the invention greatly increases the significance of the nanometer in improving the actual production efficiency.
  • the hardness of the coating is increased by more than 2 times, and the service life of the corrosive and easy-to-contact environment is increased by 4-6 times, which effectively improves the protection effect of the product.
  • portable device keyboard has small and light features, commonly used in computers, mobile phones and other equipment. It makes it easy for users to work on the journey. However, when it encounters the contamination of common liquids, such as the accidental overturn of the water cup, the soaking of rain and sweat, the inside of the keyboard is easily short-circuited and damaged. After coating with this type of nano-coating, it can ensure that the surface of the keyboard is easy to clean and function properly after being exposed to water, so that the keyboard can adapt to a more severe environment.
  • LED display has product promotion, store decoration, lighting, warning and other purposes. Some of its uses need to face the harsh environment of rain or dust, such as the rainy days, the mall's open-air LED advertising screen, road warning lights, LED display control panel in the production workshop, these harsh environments lead to LED screen failure, and easy to accumulate dust, It is difficult to clean, and after using the nano-coating, the above problems can be effectively solved.
  • fingerprint lock is a smart lock, which integrates computer information technology, electronic technology, mechanical technology and modern hardware technology, is widely used in public security criminal investigation and judicial field. However, after it meets water, its internal circuit is short-circuited, difficult to repair, and requires violent de-locking. This coating can be used to avoid this problem.
  • Some sensors need to work in a liquid environment, such as water pressure, oil pressure sensors, and sensors used in underwater operation equipment, as well as sensors that often encounter water in the working environment. These sensors use this coating. After the layer, it can guarantee that the sensor will not malfunction due to the liquid invading the internal structure of the mechanical device.
  • the silicone nano-coating prepared by the method can also be applied to the following different environments and related products:
  • Acid and alkaline solvents, acid and alkali salt spray, acid resistant atmosphere are acids and alkaline solvents, acid and alkali salt spray, acid resistant atmosphere:
  • 1 such as paraffin, olefin, alcohol, aldehyde, amine, ester, ether, ketone, aromatic hydrocarbon, hydrogenated hydrocarbon, terpene olefin, halogenated hydrocarbon, heterocyclic compound, nitrogen-containing compound and sulfur compound solvent; 2 cosmetic packaging container ; 3 fingerprint lock, headphones.
  • Resistance to cold and heat cycle (-40 ° C ⁇ +75 ° C), resistance to heat and humidity (humidity 75% ⁇ 95%): electrical, electronic, automotive electrical, such as aviation, automotive, home appliances, scientific research and other fields of equipment.
  • a method for preparing a silicone hard nano protective coating comprises the following steps:
  • the substrate is placed in a reaction chamber of the nano-coating preparation device, the reaction chamber is closed, and the reaction chamber is continuously evacuated, and the vacuum in the reaction chamber is pumped to 10 mTorr, and an inert gas Ar is introduced to open the moving mechanism. , causing the substrate to generate motion in the reaction chamber;
  • the substrate in the step (1) is a solid material, and the solid material is a block-shaped polytetrafluoroethylene sheet.
  • the reaction chamber is a rotating body chamber
  • the volume of the reaction chamber is 50 L
  • the temperature of the reaction chamber is controlled at 30 ° C
  • the flow rate of the inert gas is 5 sccm.
  • the substrate moves in the reaction chamber, and the substrate moves in the form of a circular motion of the substrate relative to the reaction chamber at a rotation speed of 3 rpm.
  • the monomer vapor component is:
  • the plasma discharge process is a low-power continuous discharge during the deposition process, specifically including the following deposition process:
  • the deposition process includes the pretreatment stage and the coating stage.
  • the plasma discharge power of the pretreatment stage is 150W, the discharge time is 450s, and then enters the coating stage.
  • the plasma discharge power is adjusted to 150W and the continuous discharge time is 600s.
  • step (2)
  • the organosilicon monomer containing a double bond structure is: 3-butenyltrimethylsilane;
  • the three polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives are: 1,4-pentadiene, ethoxylated trimethylolpropane triacrylate, ethylene glycol diacrylate;
  • the plasma discharge mode in the step (2) and the step (3) is radio frequency discharge.
  • a method for preparing a silicone hard nano protective coating comprises the following steps:
  • the substrate is placed in a reaction chamber of the nano-coating preparation device, the reaction chamber is closed, and the reaction chamber is continuously evacuated, and the vacuum in the reaction chamber is pumped to 60 mTorr, and an inert gas He is introduced to start the moving mechanism. Moving the substrate;
  • the substrate in the step (1) is a solid material, and the solid material is a bulk aluminum alloy material.
  • the reaction chamber is a cubic chamber, the volume of the reaction chamber is 250 L, the temperature of the reaction chamber is controlled at 43 ° C, and the flow rate of the inert gas is 18 sccm.
  • the substrate is subjected to planetary motion, the revolution speed is 2 rpm, and the rotation speed is 6 rpm.
  • the monomer vapor component is:
  • the plasma discharge process is a low-power continuous discharge during the deposition process, specifically including the following deposition process three times:
  • the deposition process includes a pretreatment stage and a coating stage.
  • the plasma discharge power of the pretreatment stage is 600 W, the discharge time is 60 s, and then enters the coating stage.
  • the plasma discharge power is adjusted to 10 W and the continuous discharge time is 3600 s.
  • step (2)
  • the monomer steam is introduced into the reaction chamber by atomizing and volatilizing the monomer, and is introduced into the reaction chamber by a low pressure of 60 mTorr, and the flow rate of the monomer vapor is 700 ⁇ L/min;
  • the three Si-Cl-containing silicone monomers are: methylvinyldichlorosilane, trifluoropropyltrichlorosilane, and tributylchlorosilane;
  • the four polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives are: 1,4-pentadiene, polyethylene glycol diacrylate, ethylene glycol diacrylate, diethylene glycol divinyl ether
  • the plasma discharge mode in the step (2) and the step (3) is an intermediate frequency discharge.
  • the hardness of the above aluminum alloy coating film is 4H, and its acid and alkali resistance are tested by exposure to acid and alkali environment.
  • the test results are as follows:
  • a method for preparing a silicone hard nano protective coating comprises the following steps:
  • the substrate is placed in a reaction chamber of the nano-coating preparation device, the reaction chamber is closed, and the reaction chamber is continuously evacuated, and the vacuum in the reaction chamber is drawn to 130 mTorr, and a mixture of inert gases Ar and He is introduced. a gas that activates a moving mechanism to move the substrate;
  • the substrate in the step (1) is a solid material, and the solid material is a bulk alloy steel sheet material.
  • the reaction chamber is a rotating body chamber
  • the volume of the reaction chamber is 480 L
  • the temperature of the reaction chamber is controlled at 50 ° C
  • the flow rate of the inert gas is 80 sccm.
  • the substrate was subjected to a circular motion at a rotation speed of 8 rpm.
  • the monomer vapor component is:
  • Plasma discharge, chemical vapor deposition, plasma discharge process during the deposition process is pulse discharge, specifically including the following deposition process four times:
  • the deposition process includes pretreatment stage and coating stage.
  • the plasma discharge power of the pretreatment stage is 150W, the discharge time is 450s, and then enters the coating stage.
  • the coating stage is pulse discharge, power 300W, time 600s, pulse discharge frequency is 1HZ, pulse The duty cycle is 1:1.
  • step (2)
  • the monomer steam is introduced into the reaction chamber by atomizing and volatilizing the monomer through a feed pump, and the flow rate of the monomer vapor is 580 ⁇ L/min;
  • the four Si-O-C structure-containing silicone monomers are: diphenyldiethoxysilane, dodecyltrimethoxysilane, triethylvinylsilane, hexaethylcyclotrisiloxane;
  • the polyfunctional unsaturated hydrocarbon derivative is: neopentyl glycol diacrylate
  • the volume percentage of oxygen is 37%
  • the flow rate is 60 ⁇ L/min
  • the plasma discharge is 60W
  • the continuous discharge time is 130s
  • the plasma discharge mode in the step (2) and the step (3) is high frequency discharge, and the waveform of the high frequency discharge is a bipolar pulse.
  • the above alloy steel plate material is coated with a coating hardness of 4H, immersed in an organic solvent, and tested for resistance to organic solvents.
  • the test results are as follows:
  • a method for preparing a silicone hard nano protective coating comprises the following steps:
  • the substrate is placed in a reaction chamber of the nano-coating preparation device, the reaction chamber is closed, and the reaction chamber is continuously evacuated, and the vacuum in the reaction chamber is pumped to 160 mTorr, and an inert gas He is introduced to start the moving mechanism. Moving the substrate;
  • the substrate is a solid material
  • the solid material is a bulk aluminum material and a PCB board.
  • the volume of the reaction chamber in the step (1) was 640 L, the temperature of the reaction chamber was controlled at 53 ° C, and the flow rate of the inert gas was 160 sccm.
  • step (1) the substrate is linearly reciprocated at a speed of 32 mm/min.
  • the monomer vapor component is:
  • Plasma discharge, chemical vapor deposition, plasma discharge process during the deposition process is pulse discharge, specifically including the following deposition process:
  • the deposition process includes pretreatment stage and coating stage.
  • the plasma discharge power of the pretreatment stage is 600W, the discharge time is 60s, and then enters the coating stage.
  • the coating stage is pulse discharge, power 10W, time 3600s, pulse discharge frequency is 1000HZ, pulse The duty cycle is 1:500.
  • step (2)
  • the monomer steam is introduced into the reaction chamber by atomization and volatilization, and is introduced into the reaction chamber by a low pressure of 160 mTorr, and the flow rate of the monomer vapor is 260 ⁇ L/min;
  • the three organosilicon monomers containing Si-N-Si or Si-O-Si structure are: hexamethylcyclotrisilylamino, hexamethyldisilazane, hexamethyldisiloxane;
  • the five polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives are: 1,3-butadiene, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol divinyl Ether, neopentyl glycol diacrylate;
  • the plasma discharge mode in steps (2) and (3) is microwave discharge.
  • the silicone coating deposited on the bulk aluminum material has a hardness of 4H and a silicone coating deposited on the PCB with a hardness of 2H.
  • the two coated materials are exposed to the cold and heat cycle test environment to test the cold and heat cycle impact resistance. The test results are as follows:
  • a method for preparing a silicone hard nano protective coating comprises the following steps:
  • the substrate is placed in a reaction chamber of the nano-coating preparation device, the reaction chamber is closed, and the reaction chamber is continuously evacuated, and the vacuum in the reaction chamber is pumped to 200 mTorr, and an inert gas Ar is introduced to start the moving mechanism. Moving the substrate;
  • the substrate in the step (1) is a solid material, and the solid material is an electronic component.
  • the volume of the reaction chamber in the step (1) was 1000 L, the temperature of the reaction chamber was controlled at 60 ° C, and the flow rate of the inert gas was 300 sccm.
  • the substrate was subjected to a curve reciprocating motion at a speed of 120 mm/min.
  • the monomer vapor component is:
  • Plasma discharge, chemical vapor deposition, plasma discharge process during the cycle is alternately discharged, specifically including the following deposition process three times:
  • the deposition process includes the pretreatment stage and the coating stage.
  • the plasma discharge power of the pretreatment stage is 150W
  • the continuous discharge time is 450s
  • the coating stage is the periodic alternating discharge output, power 300W, time 600s, alternating frequency At 1 Hz, the plasma cycle alternately changes the discharge output waveform to a sawtooth waveform;
  • step (2)
  • the monomer steam is introduced into the reaction chamber by atomizing and volatilizing the monomer, and is introduced into the reaction chamber by a low pressure of 200 mTorr, and the flow rate of the monomer vapor is 10 ⁇ L/min;
  • the four silicone monomers containing a cyclic structure are: bis(tritylsilyl) chromate, trifluoropropylmethylcyclotrisiloxane, 2,2,4,4-tetramethyl a group of 6,6,8,8-tetraphenylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane;
  • the three polyfunctional unsaturated hydrocarbon derivatives are: 1,4-pentadiene, tripropylene glycol diacrylate, neopentyl glycol diacrylate.
  • the volume percentage of oxygen is 23%
  • the flow rate is 80 ⁇ L/min
  • the plasma discharge is 80W
  • the continuous discharge time is 90s
  • the plasma discharge mode in the step (2) and the step (3) is a spark discharge.
  • a method for preparing a silicone hard nano protective coating comprises the following steps:
  • the substrate is placed in a reaction chamber of the nano-coating preparation device, the reaction chamber is closed, and the reaction chamber is continuously evacuated, and the vacuum in the reaction chamber is pumped to 180 mTorr, and an inert gas Ar is introduced to start the moving mechanism. Moving the substrate;
  • Step (1) The substrate is a solid material, and the solid material is an electrical component.
  • the volume of the reaction chamber in the step (1) was 780 L, the temperature of the reaction chamber was controlled at 50 ° C, and the flow rate of the inert gas was 200 sccm.
  • the substrate is subjected to planetary motion, the revolution speed is 4 rpm, and the rotation speed is 3 rpm.
  • the monomer vapor component is:
  • Plasma discharge, chemical vapor deposition, plasma discharge process is a periodic alternating discharge during deposition, specifically including the following deposition process:
  • the deposition process includes the pretreatment stage and the coating stage.
  • the plasma discharge power of the pretreatment stage is 600W
  • the continuous discharge time is 60s
  • the plasma in the coating stage is the cycle alternating discharge output, power 10W, time 3600s, alternating frequency
  • the plasma cycle alternately changes the discharge output waveform to a full-wave rectified waveform;
  • step (2)
  • the monomer steam is introduced into the reaction chamber by atomizing and volatilizing the monomer, and is introduced into the reaction chamber by a low pressure of 180 mTorr, and the flow rate of the monomer vapor is 49 ⁇ L/min;
  • silicone monomers containing a cyclic structure hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, octaphenylcyclotetrasiloxane, Diphenyldihydroxysilane;
  • the five polyfunctional unsaturated hydrocarbon derivatives are: 1,3-butadiene, isoprene, ethoxylated trimethylolpropane triacrylate, polyethylene glycol diacrylate, 1 , 6-hexanediol diacrylate;
  • the plasma discharge mode is an intermediate frequency discharge, and the waveform of the intermediate frequency discharge is sinusoidal.
  • IPX 7 test underwater 1m immersion test for 30 minutes works properly.

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Abstract

L'invention concerne un procédé de préparation d'un revêtement nanoprotecteur dur d'organosilicium, appartenant au domaine de la technologie plasma. Le procédé consiste à régler le degré de vide à l'intérieur d'une chambre de réaction, à introduire un gaz inerte, à amener un matériau de base à se déplacer, à introduire une vapeur de monomère pour le dépôt chimique en phase vapeur, et à préparer un nano-revêtement d'organosilicium par dépôt chimique en phase vapeur sur une surface du matériau de base. Le constituant de vapeur de monomère est un mélange d'au moins un monomère d'organosilicium contenant une double liaison, une structure Si-Cl, Si-O-C, Si-N-Si ou Si-O-Si ou une structure annulaire et au moins un hydrocarbure ou un dérivé d'hydrocarbure insaturé polyfonctionnel. Le procédé consiste en outre à arrêter l'introduction de la vapeur de monomère, et à introduire de l'oxygène et/ou de la vapeur d'eau pour durcir la surface du nano-revêtement d'organosilicium. La présente invention remplace les monomères composés organiques de carbone/hydrogène/oxygène classiques par le monomère d'organosilicium, chaque atome de silicium fournissant au moins 1 à 4 sites actifs pour une activité plus élevée. Une partie de l'oxygène est introduite dans le monomère, l'organosilicium est oxydé en dioxyde de silicium nanométrique, et la dureté du revêtement est considérablement augmentée par un effet de renforcement de dispersion.
PCT/CN2018/082832 2017-08-23 2018-04-12 Procédé de préparation d'un revêtement nano-protecteur dur d'organosilicium WO2019037443A1 (fr)

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