WO2019037442A1 - Procédé de préparation d'un revêtement nano-protecteur d'organosilicium - Google Patents

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

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Publication number
WO2019037442A1
WO2019037442A1 PCT/CN2018/082830 CN2018082830W WO2019037442A1 WO 2019037442 A1 WO2019037442 A1 WO 2019037442A1 CN 2018082830 W CN2018082830 W CN 2018082830W WO 2019037442 A1 WO2019037442 A1 WO 2019037442A1
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discharge
coating
reaction chamber
silicone
substrate
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PCT/CN2018/082830
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English (en)
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 WO2019037442A1 publication Critical patent/WO2019037442A1/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

Definitions

  • the invention belongs to the technical field of plasma chemical vapor deposition, and in particular relates to a preparation method of a nano protective coating.
  • Corrosive environments are the most common factor in the destruction of electronic devices. Corrosion of solid materials in electronic devices due to environmental corrosion, reduced conductor/semiconductor insulation, and short-circuit, open circuit, or poor contact.
  • the proportion of electronic components is increasing, and the requirements for moisture, mildew and corrosion resistance of electronic products are becoming more and more strict.
  • the communication frequency is constantly increasing, and the requirements for the heat dissipation of communication equipment and the stability and reliability of signal transmission are also increasing. Therefore, a reliable method is needed to effectively protect the circuit board and electronic components without affecting normal heat dissipation and signal transmission.
  • Polymer coatings are often used for material surface protection due to their economical, easy-to-coat and wide application range, which can give materials good physical and chemical durability.
  • the protective film formed on the surface of electronic appliances and circuit boards can effectively isolate the circuit board, and protect the circuit from corrosion and damage in a corrosive environment, thereby improving the reliability of the electronic device. Increased safety factor and guaranteed service life are used as anti-corrosion coatings.
  • Conformal coating is a process of applying a specific material to a PCB to form an insulating protective layer conforming to the shape of the object to be coated. It is a commonly used circuit board waterproofing method, which can effectively isolate the circuit board. And protect the circuit from the erosion and damage of harsh environments. At present, there are some problems and disadvantages in the preparation process of the conformal coating: the solvent in the liquid phase method is easy to damage the circuit board device; the high temperature of the heat curing coating is likely to cause damage to the device; the photocurable coating is difficult to be sealed inside the device. . HZO Company of the United States has developed a conformal parylene coating.
  • Parylene coating is a para-xylene polymer with low water, gas permeability and high barrier effect to achieve moisture, water and rust resistance. , the role of acid and alkali corrosion resistance. It has been found that parylene is deposited under vacuum and can be applied to fields that cannot be covered by liquid coatings such as high frequency circuits and extremely weak current systems. The thickness of the polymer film coating is the main reason for the protection failure of the para-xylene vapor-deposited conformal coating. The polymer film coating of the printed circuit board component is prone to local rust failure at a thickness of 3 to 7 microns without affecting the high. The coating thickness should be ⁇ 30 ⁇ m in the case of frequency dielectric loss.
  • Parylene coating requires high pretreatment of printed circuit boards that need protection, such as conductive components, signal transmission components, RF components, etc., in the vapor deposition of conformal coatings, it is necessary to pre-mask the circuit board components to avoid Affects component performance.
  • This drawback has brought great limitations to the application of parylene coating.
  • Pyrene coatings have high cost of raw materials, harsh coating preparation conditions (high temperature, high vacuum requirements), low film formation rate, and are difficult to be widely used.
  • thick coatings are prone to problems such as poor heat dissipation, signal transmission barriers, and increased coating defects.
  • Plasma chemical vapor deposition is a technique in which a reactive gas is excited by a plasma to promote a chemical reaction on a surface of the substrate or in a near surface space to form a solid film.
  • Plasma chemical vapor deposition coatings have the following advantages:
  • the plasma polymerization film is stable in chemical and physical properties such as solvent resistance, chemical corrosion resistance, heat resistance, and abrasion resistance.
  • the plasma polymerization film has good adhesion to the substrate.
  • a uniform film can also be formed on the surface of the substrate having irregular irregularities.
  • the coating preparation temperature is low, and can be carried out under normal temperature conditions, thereby effectively avoiding damage to temperature sensitive devices.
  • the plasma process can not only prepare a coating having a thickness of a micron order but also can prepare an ultra-thin nano-scale coating.
  • the 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 state of the substrate may result in slow deposition of coatings in some regions, 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.
  • the product industry is becoming more and more widely used.
  • 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 usually from several micrometers to several tens of micrometers.
  • Liquid-phase silicone coating technology although more environmentally friendly than traditional liquid-phase coating technology, has many shortcomings:
  • the present invention provides a method for preparing a silicone nano protective coating in order to solve the above technical problems.
  • the movement characteristics of the substrate and the plasma discharge energy are combined, and the plasma discharge energy is output while the substrate remains in a moving state.
  • Additional monomeric components with a polyfunctional crosslinked structure are introduced by plasma energy to introduce additional crosslinking sites to form a crosslinked structure.
  • 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, and 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 mutual Cross-linking, each silicon atom provides at least 1-4 active sites and has high activity. Therefore, it is easier to generate free radicals and cross-linking reaction under low temperature plasma to form dense cross-linking compounds and improve protection. performance.
  • 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.
  • a method for preparing a silicone 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 is:
  • 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 vapor is 10 to 1000 ⁇ L/min;
  • the introduction of the monomer vapor is stopped while the plasma discharge is stopped, and the reaction chamber is filled with air or an inert gas to a pressure of 2000-5000 mTorr, and then evacuated to 10-200 mTorr for the above aeration and evacuation steps. At least once, pass air to an atmospheric pressure, stop the movement of the substrate, and then remove the substrate.
  • the chemical bonds in the active monomer are controlled to break, forming higher-activity free radicals, excited free radicals and surface activation groups of mobile phones and other products.
  • the group initiates polymerization to form a nanometer waterproof film by chemical bonding, and forms a silicone nano coating on the surface of the substrate.
  • radicals are more likely to be generated and cross-linking reaction occurs in the case of low-temperature plasma to form a dense cross-linking compound.
  • 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 is 50-1000 L, the temperature of the reaction chamber is controlled at 30-60 ° C, and the flow rate of the inert gas is 5-300 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, and the waveforms of the high frequency discharge and the intermediate frequency discharge are sinusoidal or bipolar pulses.
  • the 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. At the same time, since 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 waterproof, moisture proof, mold proof, acid resistance, alkaline solvent, acid resistance, alkaline salt spray, acid resistance atmosphere, organic solvent immersion resistance, cosmetics resistance, sweat resistance, cold and heat cycle impact resistance (-40 ° C ⁇ +100 ° C), resistance to heat and humidity (humidity 75% to 95%) and other characteristics.
  • the coatings For electronic products (mobile phones, earphones, smart bracelets, etc.), drones, etc., the coatings have the above-mentioned protective performance, and the thickness of the radio frequency communication signal in the range of 10M to 8G in the range of 1 to 1000 nm The effect is less than 5%, and the coating does not affect the original heat dissipation performance of the electronic product and the current continuity requirement of the electronic product itself.
  • 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 coating structure with loose linear components, the mesh structure has better compactness and can effectively improve the corrosion-resistant environment 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 composite nano-coating with a composite structure and a gradual structure not only ensures the hydrophobicity of the film, but also improves the environmental corrosion resistance of products such as electronic products.
  • the portable keyboard has the characteristics of small and light, and is often used in computers, mobile phones and the like. 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 merchandise 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 day, the open-air LED advertising screen of the mall, the LED display control panel of the production workshop, the road warning light, the LED light module of the trademark logo, these harsh environments lead to LED The screen is out of order, and it is easy to accumulate dust and is difficult to clean. After using the nano-coating, the above problems can be effectively solved.
  • Fingerprint lock is a smart lock. It integrates computer information technology, electronic technology, mechanical technology and modern hardware technology. It 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 equipment, as well as sensors that often encounter water in the working environment. These sensors use the coating. After that, it can guarantee that the sensor will not malfunction due to the liquid invading the internal structure of the mechanical device.
  • UAV products (agricultural/civil/police): UAVs will encounter different weather conditions during normal work. Corrosive gas environment, rainy days and humid environments are inevitable, even with some pesticide reagents. s contact. After the coating is used, the drone can effectively protect it from normal use in rainy days or even in the environment of water, without the phenomenon that the circuit board is short-circuited or the flight control fails.
  • 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 ⁇ +100 ° 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 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 1 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 silicone monomer containing a double bond structure is: vinyl triethoxysilane
  • the two polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives are: 1,3-butadiene, ethylene glycol diacrylate;
  • the plasma discharge mode in the step (2) is a radio frequency discharge.
  • a method for preparing a silicone 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 anodized 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 40 ° C, and the flow rate of the inert gas is 15 sccm.
  • the substrate is subjected to planetary motion, the revolution speed is 1 rpm, and the rotation speed is 1.5 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 two Si-Cl-containing silicone monomers are: triphenylchlorosilane and trifluoropropylmethyldichlorosilane.
  • the three polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives are: 1,4-pentadiene, tripropylene glycol diacrylate, polyethylene glycol diacrylate;
  • the plasma discharge mode in the step (2) is an intermediate frequency discharge.
  • a method for preparing a silicone 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 plate material and a PC plastic plate.
  • 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 60 sccm.
  • the substrate was subjected to circular motion at a rotation speed of 3 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 three 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, and is introduced into the reaction chamber by a low pressure of 130 mTorr, and the flow rate of the monomer vapor is 550 ⁇ L/min;
  • the three Si-O-C structure-containing silicone monomers are: phenyltriethoxysilane, triethylvinylsilane, hexaethylcyclotrisiloxane;
  • the polyfunctional unsaturated hydrocarbon derivative is: 1,6-hexanediol diacrylate
  • the plasma discharge mode is a high frequency discharge, and the waveform of the high frequency discharge is a bipolar pulse.
  • a method for preparing a silicone 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 680 L, the temperature of the reaction chamber was controlled at 50 ° C, and the flow rate of the inert gas was 160 sccm.
  • the substrate is linearly reciprocated at a moving speed of 20 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 atomizing and volatilizing the monomer, and is introduced into the reaction chamber by a low pressure of 160 mTorr, and the flow rate of the monomer vapor is 220 ⁇ L/min;
  • the two silicone monomers containing Si-N-Si or Si-O-Si structure are: hexamethylcyclotrisilylamino, hexamethyldisilazane;
  • the four polyfunctional unsaturated hydrocarbons and hydrocarbon derivatives are: isoprene, ethoxylated trimethylolpropane triacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate ;
  • the plasma discharge mode in the step (2) is microwave discharge.
  • a method for preparing a silicone 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 100 mm/min.
  • the monomer vapor component is:
  • Plasma discharge, chemical vapor deposition, plasma discharge process during the deposition process is alternating periodic, specifically including the following deposition process four 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 three kinds of silicone-containing monomers having a cyclic structure are: octaphenylcyclotetrasiloxane, bis(tritylsilyl) chromate, tetramethyltetravinylcyclotetrasiloxane;
  • the five polyfunctional unsaturated hydrocarbon derivatives are: 1,4-pentadiene, tripropylene glycol diacrylate, polyethylene glycol diacrylate, ethylene glycol diacrylate, diethylene glycol Divinyl ether;
  • the plasma discharge mode in the step (2) is a spark discharge.
  • a method for preparing a silicone 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 880 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 was subjected to a curve reciprocating motion at a speed of 200 mm/min.
  • 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 35 ⁇ L/min;
  • the four Si-OC structure-containing silicone monomers are: hexaethylcyclotrisiloxane, diphenyldiethoxysilane, dodecyltrimethoxysilane, 3-chloropropyltrimethoxy Silane
  • the three polyfunctional unsaturated hydrocarbon derivatives are: polyethylene glycol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate.
  • the plasma discharge mode is an intermediate frequency discharge, and the waveform of the intermediate frequency discharge is sinusoidal.
  • IPX 7 waterproof rating test underwater 1m immersion test for 30 minutes
  • the obtained IPX 7 waterproof rating test (underwater 1m immersion test for 30 minutes) of the electrical component deposited with the waterproof and electrical breakdown coating is as follows:

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Abstract

Cette invention concerne un procédé de préparation d'un revêtement nano-protecteur d'organosilicium, appartenant au domaine de la technologie plasma. Dans le procédé, le degré de vide à l'intérieur d'une chambre de réaction est ajusté à 10-200 mTorr, un gaz inerte est introduit, un mécanisme de déplacement est mis en marche de telle sorte qu'un matériau de base se déplace, une vapeur de monomère est introduite dans la chambre de réaction pour un dépôt chimique en phase vapeur, et un nano-revêtement d'organosilicium est préparé par dépôt chimique en phase vapeur sur une surface du matériau de base. Le constituant de la vapeur de monomère est un mélange d'au moins un monomère d'organosilicium contenant une structure à double liaison Si-Cl, Si-O-C, Si-N-Si ou Si-O-Si ou une structure annulaire et au moins un hydrocarbure insaturé polyfonctionnel ou un dérivé d'hydrocarbure. La présente invention remplace les monomères composés organiques classiques de carbone/hydrogène/oxygène avec le monomère d'organosilicium, chaque atome de silicium fournissant au moins 1 à 4 sites actifs pour une activité plus élevée. L'épaisseur du revêtement peut être contrôlée avec une précision de l'ordre nanométrique à l'ordre micrométrique par l'intermédiaire du procédé de dépôt par plasma, et il n'est pas nécessaire d'utiliser un solvant. L'invention permet en outre d'éviter des inconvénients tels que la génération d'eaux usées, de déchets liquides et de gaz résiduaires produits par les procédés de revêtement d'organosilicium en phase liquide.
PCT/CN2018/082830 2017-08-23 2018-04-12 Procédé de préparation d'un revêtement nano-protecteur d'organosilicium WO2019037442A1 (fr)

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