Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/60—Deposition of organic layers from vapour phase
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/62—Plasma-deposition of organic layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
  • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
  • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
  • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
  • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/16—Antifouling paints; Underwater paints
  • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
  • C09D5/1612—Non-macromolecular compounds
  • C09D5/1625—Non-macromolecular compounds organic
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
  • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
  • C23C16/515—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using pulsed discharges
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2203/00—Other substrates
  • B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
  • B05D2203/35—Glass
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2506/00—Halogenated polymers
  • B05D2506/10—Fluorinated polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
  • B05D3/0466—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being a non-reacting gas
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
  • B05D3/0486—Operating the coating or treatment in a controlled atmosphere
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/70—Properties of coatings
  • C03C2217/76—Hydrophobic and oleophobic coatings
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2218/00—Methods for coating glass
  • C03C2218/10—Deposition methods
  • C03C2218/15—Deposition methods from the vapour phase
  • C03C2218/152—Deposition methods from the vapour phase by cvd
  • C03C2218/153—Deposition methods from the vapour phase by cvd by plasma-enhanced cvd
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic

Definitions

• the present invention relates to the field of surface coatings, and further relates to a method for forming hydrophobic surface coatings by plasma enhanced chemical vapor deposition.
• waterproof treatment can be applied to different surfaces, such as: metal, printed circuit board (PCB), fabric, electronic devices, etc., to give it performance to prevent the surface from water and liquid , Rain and other damage, extend the service life and reduce additional costs.
• PCB printed circuit board
• the monomer materials used to achieve this kind of waterproof effect are at most fluorocarbon materials. Fluorocarbon materials can form a negative charge protection at the interface due to low surface energy, strong covalent bonds, zigzag carbon chain structure and helical conformation, and are often used in textile, military, electronics and other fields. Currently, the most widely used fluorocarbon materials are perfluoroacrylates with long Rf (fluorocarbon chain length ⁇ 8). A new product is disclosed in CN101370975A. Perfluoroacrylate monomers are selected to form on the surface of fabrics such as clothes The polymer coating is preferably 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate.
• perfluoroacrylate fluorocarbon materials are mainly concentrated in a few areas, and they are mainly passed through fluorinated alcohol and acrylic. It is synthesized by a series of processes, the process is cumbersome, and the production cost is high.
• fluorite reserves are relatively abundant, followed by the refrigerant industry, especially the development of tetrafluoroethylene, hexafluoropropylene cracking technology and HFC-134a synthesis technology, which makes fluorinated
• the cost of alcohol raw materials has been rapidly reduced, and the production method has been optimized, which has strengthened the competitiveness of fluorinated alcohol products in the world market and formed a relatively complete fluorinated alcohol industry chain. This will solve certain economic cost issues.
• Plasma chemical vapor deposition technology has been widely used to form polymer coatings on different surfaces to protect the surface from damage.
• This technology uses plasma to activate the reaction gas, and this step is performed when the substrate is present.
• the plasma zone compound groups polymerize on or near the surface of the substrate.
• This technology is considered to be a dry film-forming process relative to the wet chemical method.
• the deposited film has good adhesion to the substrate, easy to design the coating structure, and good universality.
• the properties of the formed polymer coating are related to the properties of the monomer, the substrate and the coating conditions.
• the performance of the surface coating is not only related to the material and formation method of the coating itself, but also related to the nature of the substrate itself.
• the same surface coating may exhibit different properties when attached to different substrates, and for the same substrate, there may be more suitable surface coatings.
• Glass substrate is currently a widely used material, such as smart phones, tablet computers and other electronic equipment display screens.
• it is usually necessary to form a coating on the surface during processing.
• the coating materials most of the coating materials are materials that can be applied to a variety of substrates, and relatively few coatings for special substrates, such as glass substrates, make the performance of the coating material itself certain There are also limitations in the optimization of the performance of the glass substrate.
• One advantage of the present invention is to provide a hydrophobic surface coating and a preparation method thereof, which replaces perfluoroacrylate fluorocarbon materials with fluorinated alcohol compounds to reduce economic costs.
• Another advantage of the present invention is to provide a hydrophobic surface coating and a preparation method thereof, which are formed from one or more fluorinated alcohol compounds by a plasma-enhanced chemical vapor deposition method, and the manufacturing process is simplified.
• Another advantage of the present invention is to provide a hydrophobic surface coating and a preparation method thereof, wherein the surface coating formed by the fluorinated alcohol compound on the surface of the substrate has good hydrophobic properties.
• Another advantage of the present invention is to provide a hydrophobic surface coating and a preparation method thereof.
• a cross-linking agent By adding a cross-linking agent, the gas raw material is directly cross-linked in the polymerization deposition process, with high compactness, good mechanical properties, and large savings. The thermal annealing process in the large-scale production process and the resulting costs.
• Another advantage of the present invention is to provide a hydrophobic surface coating and a preparation method thereof, wherein the hydrophobic surface coating has high hydrophobicity, resistance to chemical agents, and excellent weather resistance.
• Another advantage of the present invention is to provide a hydrophobic surface coating and a preparation method thereof, which are deposited on the surface of the substrate by combining a fluorinated alcohol compound with a crosslinking agent, so that the hydrophobic surface coating and the substrate have a stronger bonding performance , It is firmer and enhances salt spray corrosion resistance.
• Another advantage of the present invention is to provide a hydrophobic surface coating and a preparation method thereof, wherein the hydrophobic surface coating is more suitable for being deposited on the surface of a glass substrate to improve the surface properties of the glass substrate.
• Another advantage of the present invention is to provide a hydrophobic surface coating and a preparation method thereof, which utilizes the material characteristics of the hydrophobic surface coating to match the material characteristics of the glass substrate, thereby making the hydrophobic surface coating and The overall performance is better when the glass substrate is combined.
• Another advantage of the present invention is to provide a hydrophobic surface coating and a preparation method thereof.
• a cross-linking agent By adding a cross-linking agent, the gas raw material is directly cross-linked in the polymerization deposition process, with high compactness, good mechanical properties, and large savings. The thermal annealing process in the large-scale production process and the resulting costs.
• Another advantage of the present invention is to provide a hydrophobic surface coating and a preparation method thereof, wherein the hydrophobic surface coating has excellent hydrophobicity, light transmittance and wear resistance.
• Another advantage of the present invention is to provide a hydrophobic surface coating and a preparation method thereof, which are deposited on the surface of the substrate by combining a fluorinated alcohol compound with a crosslinking agent, so that the hydrophobic surface coating and the substrate have a stronger bonding performance , More solid.
• the present invention provides a hydrophobic surface coating, which uses one or more fluorinated alcohol compounds as reactant gas materials and is formed on a substrate surface by a plasma enhanced chemical vapor deposition method.
• the hydrophobic surface coating wherein the fluorinated alcohol compound has a chemical formula: C n F 2n+1 -C m H 2m -OH, where n is an integer of 1-12, m It is an integer from 0-4.
• the hydrophobic surface coating wherein there are weak sites of methylene during the reaction of the fluorinated alcohol compound.
• the hydrophobic surface coating wherein the fluorinated alcohol compound is a primary alcohol.
• the hydrophobic surface coating wherein the fluorinated alcohol compound is selected from the group consisting of one or more of perfluorohexyl ethanol and perfluorobutyl ethanol.
• the hydrophobic surface coating wherein the reactive gas raw material further includes a crosslinking agent, and the crosslinking agent has the following structural formula:
• R 1 , R 2 , R 3 , R 5 , R 6 , and R 7 are selected from hydrogen, alkyl, aryl, halogen, halogenated alkyl, halogenated aryl; j and k are integers from 0 to 10 and cannot be both Is 0; R 4 is a bond, -CO-, -COO-, aryl subunit, alicyclic alkyl subunit, hydroxy substituted aliphatic alkyl subunit.
• the hydrophobic surface coating wherein the reactive gas raw material further includes a cross-linking agent
• the cross-linking agent is containing ester, ether, epoxy, cyano group Functional group compound.
• the hydrophobic surface coating wherein the reactive gas raw material further includes a crosslinking agent, and the crosslinking agent is selected from a combination: glycidyl methacrylate, allyl glycidyl One or more of glycerol ether, 1,2-epoxy-4-vinylcyclohexane, 3-(2,3-epoxypropoxy)propylvinyldimethoxysilane, and Embu ester .
• a plasma source gas is first introduced to activate the chemical deposition reaction of the reactive gas raw materials.
• the hydrophobic surface coating wherein the plasma source gas is selected from one or more of inert gases.
• Another aspect of the present invention provides a method for preparing a hydrophobic surface coating, which includes the steps of passing one or more fluorinated alcohol compound reaction gas raw materials into a reaction chamber of a plasma device, and Plasma-enhanced chemical vapor deposition is performed on the surface of a substrate in the body device to form a hydrophobic surface coating.
• the fluorinated alcohol compound in the method for preparing a hydrophobic surface coating, has a chemical formula: C n F 2n+1 -C m H 2m -OH, where n is 1 An integer of 8, and m is an integer of 2-3.
• the hydrophobic surface coating uses one or more fluorinated alcohol compounds as reactive gas materials and is formed on a substrate surface by a plasma-enhanced chemical vapor deposition method.
• the fluorinated alcohol compound has a structural formula: OH-C n H m F 2n+1-m , where n>m+1, wherein under the action of plasma, the surface of the substrate forms silanol groups.
• the present invention provides a hydrophobic surface coating which is formed from one or more fluorinated alcohols as raw materials. Further, the hydrophobic surface coating is formed on the surface of a substrate by means of plasma enhanced chemical vapor deposition by using one or more fluorinated alcohols as raw materials.
• the hydrophobic surface coating has good hydrophobicity, as well as good chemical corrosion resistance and excellent weather resistance.
• the hydrophobic surface coating has good hydrophobicity.
• the static contact angle of water is greater than 90°.
• the static contact angle ranges from 90° to 100° , 100° ⁇ 110°, 110° ⁇ 120°, 120° ⁇ 130°.
• the hydrophobic surface coating has good corrosion resistance.
• the hydrophobic surface coating is deposited on the surface of the substrate and undergoes a salt spray test for a long time, the surface of the substrate is not corroded or there are only a small number of corrosion points. , As shown in the following specific embodiments.
• the hydrophobic surface coating has a relatively small thickness and will not affect the surface use of the substrate.
• the thickness range is for example but not limited to 10-1000 nm.
• the thickness range is selected from 150 nm to 170 nm, 170 nm to 190 nm, 190 nm to 210 nm, 210 nm to 230 nm, or 230 nm to 250 nm.
• the hydrophobic surface coating is formed on the surface of the substrate by a plasma enhanced chemical vapor deposition (PECVD) process. That is, during the preparation process, the surface of the substrate is exposed to the reaction chamber of the reaction device of a plasma device, plasma is formed in the chamber, and the raw material fluorinated alcohol and/or other reactants are reacted The deposition reaction forms the hydrophobic surface coating on the surface of the substrate.
• PECVD plasma enhanced chemical vapor deposition
• the plasma-enhanced chemical vapor deposition (PECVD) process has many advantages: (1) Dry film formation does not require the use of organic solvents; (2) The etching effect of plasma on the surface of the substrate makes The deposited film has good adhesion to the substrate; (3) It can evenly deposit the coating on the surface of the irregular substrate, and the gas permeability is very strong; (4) The coating can be designed well, compared with the liquid phase method for micron level control Precision, the chemical vapor method can control the coating thickness at the nanometer scale; (5) The coating structure is easy to design, the chemical vapor method uses plasma activation, and the composite coating of different materials does not need to design a specific initiator for initiation , Through the control of input energy, a variety of raw materials can be compounded together; (6) The density is good, and the chemical vapor deposition method tends to activate multiple active sites during the plasma initiation process, similar to one in a solution reaction There are multiple functional groups on the molecule, and the molecular chains form a
• the plasma enhanced chemical vapor deposition (PECVD) process generates plasma through glow discharge, and the discharge method includes radio frequency discharge, microwave discharge, intermediate frequency discharge, electric spark discharge, and the like.
• the fluorinated alcohol compound used as the reaction raw material has the general structure C n F 2n+1 -C m H 2m -OH, where n is an integer of 1-12, and m is 0- An integer of 4. Furthermore, n is an integer of 1-8, and m is an integer of 2-3.
• reaction raw material of the fluorinated alcohol compound is selected from one or more of perfluorobutyl ethanol and perfluorohexyl ethanol.
• the raw material for the fluorinated alcohol compound reaction is a primary alcohol.
• the fluorinated alcohol compound reaction gas raw material and a crosslinking agent vapor-phase deposition react to form the hydrophobic surface coating.
• the fluorinated alcohol compound and the crosslinking agent are both reactive gas raw materials, and they are co-deposited on the surface of the substrate to form the hydrophobic surface coating.
• the crosslinker compound has the following structure:
• R 1 , R 2 , R 3 , R 5 , R 6 , and R 7 are independently selected from hydrogen, alkyl, aryl, halogen, halogenated alkyl, and halogenated aryl.
• j and k are integers from 0-10 and cannot be 0 at the same time.
• R 4 may be a bond, -CO-, -COO-, aryl subunit, alicyclic alkyl subunit, hydroxy substituted aliphatic alkyl subunit.
• the crosslinking agent may also be a multifunctional compound containing ester groups, ethers, epoxy groups, and cyano groups.
• hydrophobic surface coating wherein the crosslinking agent is from a combination: glycidyl methacrylate, allyl glycidyl ether, 1,2-epoxy-4-vinylcyclohexane , 3-(2,3-Glyoxypropoxy) propyl vinyl dimethoxy silane, emboate.
• a plasma source gas is passed into the reaction device, which is used to activate the chemical deposition reaction of the reactive gas raw materials.
• the plasma source gas is exemplified but limited to an inert gas, where the inert gas is exemplified but not limited to He and Ar.
• the plasma source gas may be a single gas or a mixture of two or more gases.
• the plasma source gas may be passed in simultaneously with the reaction gas, or may be passed in sequentially.
• the plasma source gas is introduced first, and then the reactive gas raw material is introduced.
• the plasma source gas may not be provided, that is, the fluorinated alcohol compound and/or other reactive gas raw materials are directly deposited on the surface of the substrate from the reactive gas raw material, At this time, the amount of reaction gas raw materials required increases, and to a certain extent, it will affect the reaction speed.
• the preparation process of the hydrophobic surface coating may be: preparing a hydrophobic nano coating on the surface of the substrate by using a PECVD process, placing the substrate in a vacuum or low pressure reaction chamber, and introducing plasma first
• the body source gas such as an inert gas, utilizes glow discharge to generate plasma, and then introduces the reactive gas raw materials such as the fluorinated alcohol compound to activate the reactive gas raw materials to cause a chemical vapor deposition reaction on the surface of the substrate.
• This reactive raw material can be a chemical substance that is a gas at normal temperature and pressure, or it can be a vapor formed by a liquid substance with a boiling point below 350° C. under normal pressure through decompression, heating, and the like.
• the process of preparing the hydrophobic nano coating by the plasma device includes the following steps:
• the substrate Before chemical vapor deposition on the substrate, the substrate must be cleaned. Dust, moisture, grease, etc. on the surface of the substrate will adversely affect the deposition effect. First clean the substrate with acetone or isopropanol, and then put it in a drying oven to dry.
• the plasma source gas when the plasma source gas is an inert gas or a gas that is not easy to react, the plasma source gas will not be deposited to form the hydrophobic surface coating, that is, the plasma The body source gas will not become a component of the hydrophobic surface coating, but through the interaction of the plasma source on the surface, micro-etching and other phenomena are generated, so it can clean the surface of the substrate well, and Good deposition conditions are provided for the deposition of the reactive gas raw materials, so that the deposited hydrophobic surface coating is more firmly bonded to the surface of the substrate.
• the reactant gas raw materials can be passed in at the same time as the plasma source gas, or the substrate can be pretreated for 1 to 1200s after the plasma source gas is passed in, and then the reactant gas raw materials and crosslinking agent or reaction can be passed in according to the process parameters. Gas raw materials.
• the plasma source gas is an inert gas, such as helium.
• the reaction gas raw materials are one or more fluorinated alcohol compounds.
• the substrate to be processed can be metal, PCB board, fabric, surface of electronic device, etc.
• the working power range of the plasma device is 1 to 500 W
• the pressure range is 10 mTorr to 500 mTorr
• the temperature range is 30°C to 60°C.
• a hydrophobic surface coating applied to a PCB board and a preparation method thereof go through the following steps:
• the dried PCB board is placed in a 300L plasma vacuum reaction chamber, and the reaction chamber is continuously evacuated to achieve a vacuum degree of 20 mtorr.
• the pre-treatment stage discharge power is 120W, and the discharge time is 100s.
• the reactant gas raw material perfluorohexyl ethanol is vaporized and then introduced into the reaction chamber, and chemical vapor deposition is performed on the surface of the substrate to prepare a hydrophobic surface coating.
• the monomer vapor flow rate is 150 ⁇ L/min
• the passing time is 2500s
• the discharge power is 200W
• the pulse width during discharge is 100 ⁇ s.
• a hydrophobic surface coating applied to a copper sheet and a preparation method thereof go through the following steps:
• the dried copper sheet is placed in a 500L plasma vacuum reaction chamber, and the reaction chamber is continuously evacuated to achieve a vacuum degree of 80 mtorr.
• the pre-treatment stage discharge power is 500W, and the discharge lasts for 600s.
• the reaction gas raw material perfluorobutyl ethanol is vaporized and introduced into the reaction chamber, and chemical vapor deposition is performed on the surface of the substrate to prepare a nano-coating.
• the monomer vapor flow rate is 350 ⁇ L/min
• the microwave plasma discharge the discharge power is 500W
• the continuous discharge is 600s.
• a hydrophobic surface coating applied to fabrics and a preparation method thereof go through the following steps:
• the dried fabric is placed in a 1000L plasma vacuum reaction chamber, and the reaction chamber is continuously evacuated to make the vacuum degree reach 80 mtorr.
• the pretreatment stage discharge power is 50W, and the discharge time is 300s.
• the monomer vapor flow rate was 150 ⁇ L/min
• the passing time was 3000s
• the discharge power was 100W
• the pulse width during discharge was 200 ⁇ s.
• a hydrophobic nano coating applied to electronic devices and a preparation method thereof go through the following steps:
• the dried electronic device is placed in a 1000L plasma vacuum reaction chamber, and the reaction chamber is continuously evacuated to achieve a vacuum degree of 80 mtorr.
• the plasma source gas helium gas was introduced at a flow rate of 40 sccm, and the radio frequency discharge was turned on to pre-treat the electronic device.
• the discharge power during the pre-treatment stage was 50 W and the discharge time was 300 s.
• the 1,2-epoxy-4-vinylcyclohexane (crosslinking agent) and the reactant gas raw material perfluorohexyl ethanol are vaporized and introduced into the reaction chamber at the same time, and the hydrophobic surface coating is prepared by chemical vapor deposition on the surface of the substrate .
• the monomer vapor flow rate was 320 ⁇ L/min and 150 ⁇ L/min
• the passing time was 3000s
• the discharge power was 100W
• the discharge pulse width was 200 ⁇ s.
• a hydrophobic nano coating applied to a PCB board and a preparation method thereof go through the following steps:
• the dried PCB board is placed in a 1000L plasma vacuum reaction chamber, and the reaction chamber is continuously evacuated to achieve a vacuum degree of 80 mtorr.
• the pre-treatment stage discharge power is 300W, and the discharge time is 100s.
• a hydrophobic nano-coating applied to a PCB board and a preparation method thereof go through the following steps:
• the dried PCB board is placed in a 1000L plasma vacuum reaction chamber, and the reaction chamber is continuously evacuated to achieve a vacuum degree of 80 mtorr.
• the pre-treatment stage discharge power is 300W, and the discharge time is 100s.
• the monomer vapor flow rate was 300 ⁇ L/min and 200 ⁇ L/min
• the passing time was 3000s
• the discharge power was 300W
• the discharge pulse width was 200 ⁇ s.
• PCB boards, copper sheets, fabrics, and electronic devices are used as examples to illustrate the formation process of the hydrophobic surface coating.
• Plasma-enhanced chemical vapor deposition can also be performed on other substrates to form the hydrophobic surface coating, and the present invention is not limited in this respect.
• the thickness of the hydrophobic surface coating is measured by the American Filmetrics F20-UV-film thickness measuring instrument.
• the water contact angle of the hydrophobic surface coating is tested according to the GB/T 30447-2013 standard.
• Salt spray resistance test is conducted according to GB/T 2423.18-2000 Environmental Test Method for Electrical and Electronic Products.
• Example Thickness/nm Contact angle/° Salt spray resistance test (h) Example 1 175 122 34 Example 2 155 90 10 Example 3 234 130 - Example 4 202 125 40 Example 5 198 97 35 Example 6 167 108 37
• Example 3 is fabric, and salt spray resistance test is not performed.
• hydrophobic surface coatings that can be applied to the surfaces of different substrates can be obtained.
• a hydrophobic nano-film with similar effects to the application of perfluoroacrylates was obtained.
• Adding a crosslinking agent can improve the salt spray resistance of the coating.
• the present invention provides a hydrophobic surface coating.
• the hydrophobic surface coating is formed from one or more fluorinated alcohols as raw materials. Further, the hydrophobic surface coating is formed on the surface of a substrate by means of plasma enhanced chemical vapor deposition by using one or more fluorinated alcohols as raw materials.
• the hydrophobic surface coating is suitable for being deposited on the surface of the glass substrate to improve the surface properties of the glass substrate.
• the hydrophobic surface coating has good hydrophobicity, light transmittance and wear resistance. Further, the hydrophobic surface coating has good hydrophobicity and oleophobicity.
• the static contact angle of water is greater than 100°. For example, the static contact angle ranges from 100° to 105°. °, 105° ⁇ 110°, 110° ⁇ 115°, 115° ⁇ 120°.
• the static contact angle of water is: 107°, 109°, 110°, 114°, 115°, 116°, 120°.
• the hydrophobic surface coating has good corrosion resistance. For example, when the hydrophobic surface coating is deposited on the surface of the substrate, the substrate has good wear resistance, as shown in the following specific examples.
• the hydrophobic surface coating has a relatively small thickness and will not affect the surface use of the substrate.
• the thickness range is for example but not limited to 10-1000 nm.
• the thickness range of the hydrophobic surface coating is selected from: 150 nm to 170 nm, 170 nm to 190 nm, 190 nm to 210 nm, 210 nm to 230 nm, or 230 nm to 250 nm.
• the thickness of the hydrophobic surface coating is 170 nm, 185 nm, 190 nm, 195 nm, 200 nm, 220 nm, 235 nm.
• the hydrophobic surface coating is formed on the surface of the substrate by a plasma enhanced chemical vapor deposition (PECVD) process. That is, during the preparation process, the surface of the substrate is exposed to the reaction chamber of the reaction device of a plasma device, plasma is formed in the chamber, and the raw material fluorinated alcohol and/or other reactants are reacted The deposition reaction forms the hydrophobic surface coating on the surface of the substrate.
• PECVD plasma enhanced chemical vapor deposition
• the plasma-enhanced chemical vapor deposition (PECVD) process has many advantages: (1) Dry film formation does not require the use of organic solvents; (2) The etching effect of plasma on the surface of the substrate makes The deposited film has good adhesion to the substrate; (3) It can evenly deposit the coating on the surface of the irregular substrate, and the gas permeability is very strong; (4) The coating can be designed well, compared with the liquid phase method for micron level control Precision, the chemical vapor method can control the coating thickness at the nanometer scale; (5) The coating structure is easy to design, the chemical vapor method uses plasma activation, and the composite coating of different materials does not need to design a specific initiator for initiation , Through the control of input energy, a variety of raw materials can be compounded together; (6) The density is good, and the chemical vapor deposition method tends to activate multiple active sites during the plasma initiation process, similar to one in a solution reaction There are multiple functional groups on the molecule, and the molecular chains form a
• the plasma enhanced chemical vapor deposition (PECVD) process generates plasma through glow discharge, and the discharge method includes radio frequency discharge, microwave discharge, intermediate frequency discharge, electric spark discharge, and the like.
• the fluorinated alcohol compound as the reaction raw material has the general structure OH-C n H m F 2n+1-m , where n>m+1.
• the fluorinated alcohols with the general structure OH-C n H m F 2n+1-m and n>m+1 are more suitable to be deposited on glass substrates by plasma enhanced chemical vapor deposition.
• plasma acts on the surface of the glass to form silanol groups on the surface, which is easy to interact with the hydroxyl groups in the raw material fluorinated alcohol, so that the hydrophobic surface coating and the substrate surface are more firmly bonded, thereby Reflects more excellent surface properties.
• the material structure of the substrate exhibits the nature of a hydroxyl group after being processed, the fluorinated alcohol compound conforming to the above general formula and the substrate can easily form the more excellent hydrophobic surface coating.
• the raw material for the fluorinated alcohol compound reaction is selected from: perfluorohexyl ethanol, perfluorobutyl ethanol, perfluorobutyl propanol, perfluorohexyl propanol, 1,2,3,3,4,4, 5,5,6,6,6-Undecafluorohexan-1-ol, 3-(difluoromethyl)-2,3,4,4,4-pentafluoro-2-(trifluoromethyl ) One or more of -butan-1-ol.
• the fluorinated alcohol compound reaction gas raw material reacts with a crosslinking agent through vapor deposition reaction to form the hydrophobic surface coating.
• the fluorinated alcohol compound and the crosslinking agent are both reactive gas raw materials, and they are co-deposited on the surface of the substrate to form the hydrophobic surface coating.
• the crosslinker compound has the following structure:
• R 1 , R 2 , R 3 , R 5 , R 6 , and R 7 are independently selected from hydrogen, alkyl, aryl, halogen, halogenated alkyl, and halogenated aryl.
• j and k are integers from 0-10 and cannot be 0 at the same time.
• R 4 may be a bond, -CO-, -COO-, aryl subunit, alicyclic alkyl subunit, hydroxy substituted aliphatic alkyl subunit.
• the crosslinking agent may also be a multifunctional compound containing ester groups, ethers, epoxy groups, and cyano groups.
• hydrophobic surface coating wherein the crosslinking agent is from a combination: glycidyl methacrylate, allyl glycidyl ether, 1,2-epoxy-4-vinylcyclohexane , 3-(2,3-Glyoxypropoxy) propyl vinyl dimethoxy silane, emboate.
• a plasma source gas is passed into the reaction device, which is used to activate the chemical deposition reaction of the reactive gas raw materials.
• the plasma source gas is exemplified but not limited to an inert gas, and the inert gas is exemplified but not limited to He and Ar.
• the plasma source gas can be a single gas or a mixture of two or more gases.
• the plasma source gas can be passed in at the same time as the reactive gas raw material, or can be passed in sequentially.
• the plasma source gas is introduced first, and then the reactive gas raw material is introduced.
• the plasma source gas may not be provided, that is, the fluorinated alcohol compound and/or other reactive gas raw materials are directly deposited on the surface of the substrate from the reactive gas raw material, At this time, the amount of reaction gas raw materials required increases, and to a certain extent, it will affect the reaction speed.
• the preparation process of the hydrophobic surface coating may be: preparing a hydrophobic nano coating on the surface of the substrate by using a PECVD process, placing the substrate in a vacuum or low pressure reaction chamber, and introducing plasma first
• the body source gas such as an inert gas, utilizes glow discharge to generate plasma, and then introduces reactive gas raw materials such as the fluorinated alcohol compound to activate the reactive gas raw materials to cause a chemical vapor deposition reaction on the surface of the substrate.
• This reactive raw material can be a chemical substance that is a gas under normal temperature and pressure, or it can be a vapor formed by a liquid substance with a boiling point lower than 350°C under normal pressure through decompression, heating, etc.
• the process of preparing the hydrophobic nano coating by the plasma device includes the following steps:
• the substrate Before chemical vapor deposition on the substrate, the substrate must be cleaned. Dust, moisture, grease, etc. on the surface of the substrate will adversely affect the deposition effect. First clean the substrate with acetone or isopropanol, and then put it in a drying oven to dry.
• the plasma source gas when the plasma source gas is an inert gas or a gas that is not easy to react, the plasma source gas will not be deposited to form the hydrophobic surface coating, that is, the plasma The body source gas will not become a component of the hydrophobic surface coating, but through the interaction of the plasma source on the surface, micro-etching and other phenomena are generated, so the surface of the substrate can be cleaned well, and Good deposition conditions are provided for the deposition of the reactive gas raw materials, so that the deposited hydrophobic surface coating is more firmly bonded to the surface of the substrate.
• the reactive gas raw materials can be passed in at the same time as the plasma source, or the substrate can be pretreated for 1 to 1200s after the plasma source is passed in, and then the reactive gas raw materials and crosslinking agent or reactive gas raw materials can be passed in according to the process parameters. .
• the plasma source gas is an inert gas such as helium and argon.
• the reaction gas raw materials are one or more fluorinated alcohol compounds.
• the substrate to be processed is preferably a glass substrate.
• the working power range of the plasma device is 1 to 500 W
• the pressure range is 10 mTorr to 500 mTorr
• the temperature range is 30°C to 60°C.
• a hydrophobic surface coating applied to a glass substrate and a preparation method thereof go through the following steps:
• the dried glass substrate is placed in a 1000L plasma vacuum reaction chamber, and the reaction chamber is continuously evacuated to achieve a vacuum degree of 80 mtorr.
• the plasma source gas argon
• the pre-treatment stage had a discharge power of 50 W and a discharge time of 300 s.
• the reactant gas raw material perfluorobutyl ethanol is vaporized and then introduced into the reaction chamber, and chemical vapor deposition is performed on the surface of the substrate to prepare a hydrophobic surface coating.
• the monomer vapor flow rate is 260 ⁇ L/min
• the discharge time is 3300s
• the pulse width during discharge is 3ms
• the discharge power is 100W.
• Example a1 Under the same conditions as in Example a1, the glass substrate was replaced with a PCB board, and the coating process was performed.
• a hydrophobic surface coating applied to a glass substrate and a preparation method thereof go through the following steps:
• the dried glass substrate is placed in a 1000L plasma vacuum reaction chamber, and the reaction chamber is continuously evacuated to achieve a vacuum degree of 100 mtorr.
• the plasma source gas argon
• the plasma source gas was introduced at a flow rate of 20 sccm, and radio frequency discharge was turned on to pre-treat the glass substrate.
• the discharge power during the pre-treatment stage was 200 W and the discharge lasted 600 s.
• the reactant gas raw material perfluorohexyl ethanol is vaporized and then introduced into the reaction chamber, and chemical vapor deposition is performed on the surface of the glass substrate to prepare a nano coating.
• the monomer steam flow rate is 500 ⁇ L/min
• the discharge power is 300W
• the discharge time is 2500s
• the discharge pulse width is 100us.
• Example a2 Under the same conditions as in Example a2, the glass substrate was replaced with a PCB board, and the coating process was performed.
• a hydrophobic surface coating applied to a glass substrate and a preparation method thereof go through the following steps:
• the dried glass substrate is placed in a 1000L plasma vacuum reaction chamber, and the reaction chamber is continuously evacuated to achieve a vacuum degree of 40 mtorr.
• the plasma source gas helium gas was introduced at a flow rate of 40 sccm, and the microwave discharge was turned on to pretreat the glass substrate.
• the discharge power during the pretreatment stage was 500 W and the discharge time was 600 s.
• the reaction gas raw material perfluorobutyl propanol is vaporized and introduced into the reaction chamber, and chemical vapor deposition is performed on the surface of the substrate to prepare a nano-coating.
• the monomer steam flow rate was 400 ⁇ L/min
• the microwave discharge power was 500W
• the discharge time was 1200s.
• Example a3 Under the same conditions as in Example a3, the glass substrate was replaced with a PCB board, and the coating process was performed.
• a hydrophobic nano-coating applied to a glass substrate and a preparation method thereof go through the following steps:
• the dried glass substrate is placed in a 1000L plasma vacuum reaction chamber, and the reaction chamber is continuously evacuated to achieve a vacuum degree of 40 mtorr.
• the plasma source gas helium gas was introduced at a flow rate of 40 sccm, and the microwave discharge was turned on to pretreat the glass substrate.
• the discharge power during the pretreatment stage was 500 W and the discharge time was 600 s.
• the reactant gas raw material perfluorohexyl propanol is vaporized and simultaneously introduced into the reaction chamber, and chemical vapor deposition is performed on the surface of the substrate to prepare a hydrophobic surface coating.
• the monomer steam flow rate was 350 ⁇ L/min
• the microwave discharge power was 500W
• the discharge time was 1200s.
• Example a4 Under the same conditions as in Example a4, the glass substrate was replaced with a PCB board, and the coating process was performed.
• a hydrophobic nano coating applied to a glass substrate and a preparation method thereof go through the following steps:
• the dried glass substrate is placed in a 1000L plasma vacuum reaction chamber, and the reaction chamber is continuously evacuated to achieve a vacuum degree of 300 mtorr.
• the plasma source gas argon was introduced at a flow rate of 80 sccm, and radio frequency discharge was turned on to pretreat the glass substrate.
• the discharge power during the pretreatment stage was 500W and the discharge time was 3000s.
• the reaction gas raw material 1,2,3,3,4,4,5,5,6,6,6-undecafluoro-hexan-1-ol is vaporized and introduced into the reaction chamber, and chemical vapor is carried out on the surface of the substrate Deposition to prepare a hydrophobic surface coating.
• the monomer steam flow rate was 1000 ⁇ L/min
• the continuous discharge time was 3000s
• the discharge power was 500W.
• Example a5 Under the same conditions as in Example a5, the glass substrate was replaced with a PCB board, and the coating process was performed.
• a hydrophobic nano coating applied to a glass substrate and a preparation method thereof go through the following steps:
• the dried glass substrate is placed in a 1000L plasma vacuum reaction chamber, and the reaction chamber is continuously evacuated to achieve a vacuum degree of 80 mtorr.
• the pre-treatment stage discharge power is 500W
• the discharge time is 3000s.
• the reaction gas raw material 3-(difluoromethyl)-2,3,4,4,4-pentafluoro-2-(trifluoromethyl)-butan-1-ol is vaporized and introduced into the reaction chamber at the same time. Chemical vapor deposition is performed on the surface of the material to prepare a hydrophobic surface coating.
• the monomer vapor flow rate was 1000 ⁇ L/min
• the continuous discharge time was 3000s
• the discharge power was 500W.
• Example a6 Under the same conditions as in Example a6, the glass substrate was replaced with a PCB board, and the coating process was performed.
• Example a6 Under the same conditions as in Example a6, the crosslinking agent 3-(2,3-glycidoxy)propylvinyldimethoxysilane was added to the reaction gas raw material to perform the coating process.
• the cross-linking agent glycidyl methacrylate was added to the reaction gas raw material to perform the coating process.
• the thickness of the hydrophobic surface coating is measured by the American Filmetrics F20-UV-film thickness measuring instrument.
• the water contact angle of the hydrophobic surface coating is tested according to the GB/T 30447-2013 standard.
• the abrasion resistance of the hydrophobic surface coating is tested by XM-860 abrasion tester.
• the light transmittance of the hydrophobic surface coating was measured with the British Lambda950 UV spectrophotometer.
• Example Thickness/nm Contact angle/° Wear resistance (number of cycles) Transmittance/%
• Example a1 195 114 2500 95 Comparative Example a1 180 108 2000 90
• Example a5 235 120 2200 95 Comparative Example a5 220 115 2000 91
• Example a6 200 110 2600 93 Comparative Example a6 193 105 2300 90
• a1-a6 preferably different fluorinated alcohol fluorocarbon compounds are used as reactive gas raw materials, and the hydrophobic surface coating is deposited on the surface of the glass substrate under predetermined conditions through a plasma-enhanced chemical deposition method, It can be seen from the test results that the overall test results of the hydrophobic surface coating formed on the surface of the glass substrate in each embodiment show that the static contact angle of water is large, that is, it has good hydrophobic properties and good resistance. Abrasive.
• the comparative examples a1-a6 and the corresponding examples a1-a6 are respectively deposited on the PCB board as the substrate under the same conditions to form a hydrophobic surface coating.
• the gas raw materials are basically the same conditions. When PCB substrates are selected, their hydrophobicity and wear resistance are weakened, which means that the reactive gas raw materials are more suitable for deposition on glass substrates, or when they are matched with glass substrates Better performance.
• Example a7 and a8 different cross-linking agents were added under the same conditions as in Example a6. From the comparison of Examples a6, a7 and a8, it can be seen that the addition of the cross-linking agent can to a certain extent The performance of the hydrophobic surface coating is further optimized.
• the fluorinated alcohols conforming to the predetermined general formula are used as the raw material of the reaction gas, and the hydrophobic surface coating is deposited on the surface of the glass substrate.
• the characteristics of the alcohols cooperate with the glass substrate to form a surface coating with better performance, which has a better surface modification effect than other deposition materials or other substrates, and in some embodiments, crosslinking is added
• the agent can further improve the performance of the coating.

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