CN111570216B - Composite protective film layer with silane transition layer, preparation method thereof and product - Google Patents
Composite protective film layer with silane transition layer, preparation method thereof and product Download PDFInfo
- Publication number
- CN111570216B CN111570216B CN202010342097.XA CN202010342097A CN111570216B CN 111570216 B CN111570216 B CN 111570216B CN 202010342097 A CN202010342097 A CN 202010342097A CN 111570216 B CN111570216 B CN 111570216B
- Authority
- CN
- China
- Prior art keywords
- silane
- corrosion inhibitor
- transition layer
- protective film
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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
- B05D1/62—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
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/60—Deposition of organic layers from vapour phase
-
- 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
- B05D3/14—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 electrical means
- B05D3/141—Plasma treatment
- B05D3/142—Pretreatment
-
- 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
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
-
- 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
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- 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
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- 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
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
-
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- 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
-
- 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
- B05D2252/00—Sheets
Abstract
The composite protective film layer with the silane transition layer comprises a silane transition layer and a coating layer, wherein the silane transition layer is formed by organic silane through plasma chemical vapor deposition, wherein after the silane transition layer is formed, the coating layer is formed by first monomer and second monomer through plasma chemical vapor deposition on the silane transition layer, wherein the first monomer is one or two selected from low-dipole moment organic monomers and multifunctional acrylate compounds, and the second monomer is a fluorocarbonate compound.
Description
Technical Field
The invention relates to the technical field of surface treatment, in particular to a composite protective film layer with a silane transition layer, a preparation method and a product thereof.
Background
Three-protection, namely mould proof, moisture proof and salt fog proof, is a very important issue for electronic equipment in the process of storage, transportation and use. Once the safeguards are not in place, the electronic device may fail because of a short circuit caused by any of these problems.
At present, the protective film layer is used for protecting the electronic product, and is an effective measure for coping with the three-proofing problem. The protective film layer is prepared on the surface of the electronic product by a specific method, and there are two general methods, one is a liquid phase preparation method and the other is a gas phase preparation method. The former method forms a dense organic coating on the surface of an electronic product by thermal curing or photo curing. However, waste water, waste gas and waste liquid are generated in the production process, and the used solvent can cause a certain damage to the electronic products. Most of the film layers prepared by the liquid phase preparation method are tens of micrometers in thickness, and influence is caused on heat dissipation and signal transmission of electronic products.
The most typical application of the latter method is evaporation of a parylene coating, which is a polymer of para-xylene. In this manner, paraxylene is first heated to 680 degrees celsius to form active paraxylene dimers, and then the temperature is reduced to enable the polymer to be deposited on the electronic product surface to form a polymer coating. However, parylene needs to be prepared by deposition under vacuum conditions, that is, the conditions for coating preparation require high temperatures and high vacuum. In addition, similar to the liquid phase method, the film thickness of the vapor deposition parylene coating needs to be tens of micrometers, and if the film thickness is smaller, the protective performance of the film on the electronic product is affected.
Furthermore, the film layer is prepared by adopting a liquid phase preparation method or a method for evaporating a parylene coating, the selectivity of the parylene coating to raw material monomers is poor, most of the prepared film layer is a single film layer, and the protection requirements on electronic products in different environments are difficult to meet.
Disclosure of Invention
The invention has the advantages that the composite protective film layer with the silane transition layer, the preparation method and the product thereof are provided, wherein the composite protective film layer has lower requirements on preparation conditions and is suitable for popularization and application.
Another advantage of the present invention is to provide a composite protective film layer having a silane transition layer, and a method and product for making the same, wherein the thickness of the composite protective film layer can be made thinner, such as on the order of nanometers, and still provide better protective performance at thinner thicknesses.
The invention further provides a composite protective film layer with a silane transition layer, a preparation method and a product thereof, wherein the composite protective film layer is prepared by adopting a plasma chemical vapor deposition method and can be suitable for various raw material monomers.
The invention further provides a composite protective film layer with a silane transition layer, a preparation method and a product thereof, wherein the composite protective film layer is prepared by adopting a plasma chemical vapor deposition method, has low preparation temperature, is suitable for preparing various types of electronic equipment, and does not damage the electronic equipment in the preparation process.
Another advantage of the present invention is to provide a composite protective film layer having a silane transition layer, and a method of manufacturing the same, and a product thereof, wherein the composite protective film layer includes a silane transition layer and a coating layer, wherein the silane transition layer can improve a bonding force between the composite protective film layer and an electronic device.
Another advantage of the present invention is to provide a composite protective film having a silane transition layer that can improve the corrosion resistance of the composite protective film, and methods and products for making the same.
Another advantage of the present invention is to provide a composite protective film layer having a silane transition layer, and a method for preparing the same, and a product thereof, wherein the composite protective film layer is crosslinked to form a dense network structure by introducing a plurality of functional groups to form a plurality of active sites in a plasma discharge environment, so as to improve corrosion resistance and stability.
The invention further provides a composite protective film layer of the silane transition layer, a preparation method and a product thereof, wherein the preparation method reduces the phenomenon of mutual reaction of raw material monomers in a single channel in the traditional preparation method by a multi-channel feeding mode.
According to one aspect of the present invention, there is provided a composite protective film having a silane transition layer, comprising:
A silane transition layer, wherein the silane transition layer is formed by plasma chemical vapor deposition from organosilane; and
a coating, wherein after forming the silane transition layer, the coating is formed on the silane transition layer by plasma chemical vapor deposition from a first monomer and a second monomer, wherein the first monomer is one or two selected from a low dipole moment organic monomer and a multifunctional acrylate compound, and wherein the second monomer is a fluorocarbonate compound.
According to at least one embodiment of the present invention, the silane transition layer is deposited on a surface of a substrate.
According to at least one embodiment of the present invention, the silane transition layer is formed from hydrophobic silane and/or hydrophilic silane by plasma chemical vapor deposition.
According to at least one embodiment of the present invention, the silane transition layer is formed by plasma chemical vapor deposition from an organosilane and a corrosion inhibitor, wherein the corrosion inhibitor is an organic corrosion inhibitor, and the organic corrosion inhibitor is selected from one or more of imidazole and its salts, quinoline and its salts, pyrimidine and its salts, benzotriazole and its derivatives, and organic amines. Alternatively, the corrosion inhibitor is an inorganic corrosion inhibitor, wherein the inorganic corrosion inhibitor is a rare earth nitrate.
According to at least one embodiment of the invention, the corrosion inhibitor is an organic corrosion inhibitor, wherein the organic corrosion inhibitor is selected from the group consisting of: one or more of benzotriazole, benzimidazole, 2-thio-1-methylimidazole, dimercaptothiadiazole, 1-phenyl-4-methylimidazole, pyrazoline, tetrazole, uracil, 5-aminouracil, dithiouracil, N- (2-furfuryl) -p-toluidine, N- (5-methyl-2-furfuryl) -p-toluidine and hydroxyquinoline
According to at least one embodiment of the invention, the inorganic corrosion inhibitor is selected from the group consisting of: lanthanum nitrate, cerium nitrate, molybdenum nitrate, erbium nitrate, zirconium nitrate, cobalt nitrate, yttrium nitrate, scandium nitrate and one or more of indium nitrate.
According to at least one embodiment of the invention, the slow release agent is an organic slow release agent and is selected from the group consisting of: one or more of benzotriazole, dithiouracil and dimercaptothiadiazole.
According to at least one embodiment of the invention, the inorganic slow release agent is selected from the group consisting of: one or more of lanthanum nitrate and cerium nitrate.
According to at least one embodiment of the present invention, the organosilane has the formula Y-R-SiX 3 Wherein Y is one of ureido, carboxylic acid, ether, amino, hydrocarbyl, thio, ester, phenyl, epoxy, wherein R is an organic And a carbon chain, wherein X is selected from one of an oxygen-bearing group, a halogen group and a nitrogen-bearing group.
According to at least one embodiment of the present invention, R comprises one of C-C, C = C, C-N-C, C-S-C.
According to at least one embodiment of the present invention, X is one of methoxy, ethoxy, chloro, bromo, acetoxy, amino.
According to at least one embodiment of the invention, the organosilane comprises a hydrophilic silane and is selected from the group consisting of: one or more of ureidopropyl triethoxysilane, ureidopropyl trimethoxysilane, aminopropyl triethoxysilane, aminopropyl trimethoxysilane, 2-aminoethyl-aminopropyl trimethoxysilane, diethylenetriaminopropyl trimethoxysilane, aminoethylaminopropyl methyldimethoxy silane and diethylenetriaminopropyl trimethoxysilane.
According to at least one embodiment of the invention, the organosilane is selected from the group consisting of: one or more of ureidopropyl trimethoxysilane and 2-aminoethyl-aminopropyl trimethoxysilane.
According to at least one embodiment of the invention, the organosilane comprises a hydrophobic silane and is selected from the group consisting of: phenyl triethoxysilane, vinyl propyl trimethoxysilane, vinyl triethoxysilane, vinyl trimethylsilane, 3-butenyltrimethylsilane, vinyl tributylketoximosilane, tetramethyl divinyl disiloxane, 1, 2-trifluoro vinyl triphenylsilane, hexaethyl cyclotrisiloxane, 3- (methacryloyloxy) propyl trimethoxysilane, phenyl tris (trimethylsiloxy) silane, diphenyl diethoxysilane, triphenylchlorosilane, methyl vinyl dichlorosilane, trifluoropropyl trichlorosilane, trifluoropropyl methyldichlorosilane, dimethylphenyl chlorosilane, tributylchlorosilane, benzyl dimethylchlorosilane, hexamethylcyclotrisiloxane, octamethyl cyclotetrasiloxane, hexaphenyl cyclotrisiloxane, octaphenyl cyclotetrasiloxane, triphenylhydroxy silane, diphenyl dihydroxy silane, trifluoropropyl methyl cyclotrisiloxane, 2, 4-tetramethyl-6,6,8,8-tetraphenyl cyclotetrasiloxane, tetramethyl tetravinylcyclotrisiloxane, 3-glycidoxy-triethoxy-propyl, gamma-trimethoxy-propyl siloxane, and gamma-trimethoxy-propyl-siloxane.
According to at least one embodiment of the invention, the organosilane is selected from the group consisting of: one or more of hexamethyl cyclotrisiloxane, octamethyl cyclotrisiloxane, tetramethyl tetravinyl cyclotrisiloxane and thiopropyl trimethoxy silane.
According to at least one embodiment of the invention, the first monomer comprises a low dipole moment organic compound selected from the group consisting of: para-xylene, benzene, toluene, carbon tetrafluoride, alpha-methylstyrene, poly-para-xylene, dimethylsiloxane, polydimethylsiloxanes of 500-50000 molecular weight, allyl benzene, decafluorobiphenyl ketone, perfluoroallyl benzene, tetrafluoroethylene, hexafluoropropylene, 1H-perfluorooctylamine, perfluoroiodododecane, perfluorotributylamine, 1, 8-diiodoperfluorooctane, perfluorohexyl iodoane, perfluoroiodobutane, perfluoroiododecane, perfluorooctyl iodoane, 1, 4-bis (2 ',3' -epoxypropyl) perfluorobutane, dodecafluoro-2-methyl-2-pentene, 2- (perfluorobutyl) ethyl methacrylate, 2- (perfluorooctyl) ethyl iodide, perfluorodecyl ethyl iodide, 1, 2-tetrahydroperfluorohexyl iodide, perfluorobutyl ethylene one or more of 1H, 2H-perfluoro-1-decene, 2,4, 6-tris (perfluoroheptyl) -1,3, 5-triazine, perfluorohexyl ethylene, 3- (perfluoro-n-yl) -1, 2-propylene oxide, perfluorocyclic ether, perfluorododecyl ethylene, perfluorododecyl ethyl iodide, dibromo-p-xylene and 1, 4-tetraphenyl-1, 3-butadiene.
According to at least one embodiment of the invention, the first monomer comprises a polyfunctional acrylate compound selected from the group consisting of: diethylene glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol dimethacrylate, pentafluorophenol acrylate, tripropylene glycol diacrylate, triethylene glycol dimethacrylate, dimethylaminoethyl methacrylate, allyl methacrylate, t-butyl methacrylate, glycidyl methacrylate, trimethylsilyl methacrylate and diethylene glycol dimethacrylate.
According to at least one embodiment of the present invention, the second monomer comprises a fluorocarbonate compound selected from the group consisting of: 3- (perfluoro-5-methyl hexyl) -2-hydroxypropyl methacrylate, 2- (perfluorodecyl) ethyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate, 2- (perfluorododecyl) ethyl acrylate, 2-perfluorooctyl ethyl acrylate, 1H, 2H-perfluorooctanol acrylate, 2- (perfluorobutyl) ethyl acrylate, (2H-perfluoropropyl) -2-acrylate, (perfluorocyclohexyl) methacrylate, 3-trifluoro-1-propyne, 1-ethynyl-3, 5-difluorobenzene or 4-ethynyl trifluorotoluene.
According to another aspect of the present invention, there is provided a coated product, wherein the product is coated with a composite protective film layer having a silane transition layer by plasma chemical vapor deposition, wherein an organosilane forms the silane transition layer of the composite protective film layer on the surface of the product by plasma chemical vapor deposition, and then after the silane transition layer is formed, a coating layer is formed on the surface of the product coated with the silane transition layer by plasma chemical vapor deposition from a first monomer and a second monomer to form the composite protective film layer, wherein the first monomer is one or both selected from a low dipole moment organic monomer and a multifunctional acrylate compound, and wherein the second monomer is a fluorocarbonate compound.
According to at least one embodiment of the invention, the product is selected from one or more of a combination electronic product, a silk product, a metal product, a glass product, a ceramic product.
According to another aspect of the present invention, there is provided a method for preparing a composite protective film layer having a silane transition layer, comprising the steps of:
forming a silane transition layer on the surface of a substrate through plasma chemical vapor deposition; and
And forming a coating layer by plasma chemical vapor deposition after the silane transition layer is formed so as to form a composite protective film layer with the silane transition layer.
According to at least one embodiment of the present invention, the depositing a silane transition layer step further comprises the steps of:
introducing auxiliary gas into a reaction cavity of a reaction device; and
and then introducing an organosilane raw material into the reaction cavity to form the silane transition layer on the surface of the substrate in a plasma environment.
According to at least one embodiment of the present invention, in the depositing the coating layer, a first monomer and a second monomer are introduced into a reaction chamber of a reaction apparatus to form the coating layer in a plasma environment, wherein the first monomer is a low dipole moment organic monomer and/or a polyfunctional acrylate compound, and wherein the second monomer is a fluorocarbonate compound.
According to at least one embodiment of the present invention, in the above method, the deposition of the silane transition layer and the coating layer respectively includes a pretreatment stage in which the plasma discharge power is 120 to 500W for a discharge time of 60 to 500s and a plating stage in which the plasma discharge power is 10 to 180W for a discharge time of 400 to 7200s.
According to at least one embodiment of the present invention, in the above method, the plasma discharge mode is an electrodeless discharge, a single electrode discharge, a double electrode discharge, or a multi-electrode discharge.
According to at least one embodiment of the present invention, in the above method, the silane transition layer is prepared from an organosilane and a corrosion inhibitor solution as raw materials.
According to at least one embodiment of the present invention, in the above method, the organosilane includes a hydrophilic silane and a hydrophobic silane in a mass ratio of 0 to 100 parts and 50 to 100 parts.
Detailed Description
The following description is presented to enable one of ordinary skill in the art to make and use the invention. The preferred embodiments in the following description are by way of example only and other obvious variations will occur to those skilled in the art. The basic principles of the invention defined in the following description may be applied to other embodiments, variations, modifications, equivalents, and other technical solutions without departing from the spirit and scope of the invention.
It will be understood that the terms "a" and "an" should be interpreted as referring to "at least one" or "one or more," i.e., in one embodiment, the number of elements may be one, while in another embodiment, the number of elements may be plural, and the term "a" should not be interpreted as limiting the number.
The invention provides a composite protective film layer with a silane transition layer, wherein the composite protective film layer comprises a silane transition layer and a coating layer, wherein the silane transition layer is firstly prepared on the surface of a substrate by a plasma chemical vapor deposition method, and then the coating layer is prepared on the surface of the silane transition layer, that is, the silane transition layer is positioned between the surface of the substrate and the coating layer.
The silane transition layer can be prepared from hydrophobic silane and hydrophilic silane which are respectively used as raw materials, or can be prepared from the hydrophobic silane and the hydrophilic silane which are jointly used as raw materials. In particular, when the silane transition layer is made of a hydrophobic silane and a hydrophilic silane together as raw materials, the hydrophilic silane may bond between the metal substrate and the coating layer, and the hydrophobic silane may enhance the hydrophobic property of the silane transition layer itself.
Further, the silane raw material of the silane transition layer can be doped with a corrosion inhibitor, wherein the addition of the corrosion inhibitor can provide the corrosion resistance of the silane transition layer.
For the whole composite protective film, the silane transition layer can play a protective role on the inner side of the coating, so that the corrosion resistance of the whole substrate is improved.
The invention provides a product with the composite protective film layer of the silane transition layer, wherein the product can be an electronic product, a silk fabric, a woven bag, a metal surface, a glass surface, a ceramic surface and the like. That is, when the composite protective film layer is attached to the surface of an electronic product, a silk fabric, a woven bag, a metal product, a glass product or a ceramic product, the composite protective film layer can protect the product, for example, the product has better corrosion resistance.
The invention provides a preparation method of a composite protective film layer with a silane transition layer, wherein the composite protective film layer is formed on the surface of a substrate through a plasma enhanced chemical vapor deposition process. That is, during the preparation process, the substrate surface is exposed to a reaction chamber of a plasma enhanced chemical vapor deposition reaction apparatus, a plasma is formed in the reaction chamber, and then the silane transition layer is formed on the substrate surface through a silane raw material deposition reaction. And then forming the coating layer outside the silane transition layer through a reaction raw material deposition reaction for preparing the coating layer, thereby obtaining the composite protective film layer with the silane transition layer.
The plasma enhanced chemical vapor deposition process has many advantages over other existing deposition processes: (1) dry film formation does not require the use of an organic solvent; (2) The etching effect of the plasma on the surface of the substrate ensures that the deposited film has good adhesion with the substrate; (3) The surface of the irregular matrix can be uniformly deposited with a coating film, and the gas phase permeability is extremely strong; (4) The coating has good designability, compared with the micron-scale control precision of a liquid phase method, the chemical vapor phase method can control the thickness of the coating on the nanometer scale; (5) The coating structure is easy to design, the chemical vapor phase method uses plasma for activation, the composite coating of different materials is not required to be designed with a specific initiator for initiation, and various raw materials can be compounded together through the regulation and control of input energy; (6) The compactness is good, a plurality of active sites are often activated in the plasma initiation process by a chemical vapor deposition method, and the method is similar to the solution reaction that one molecule is provided with a plurality of functional groups, and a cross-linking structure is formed among molecular chains through the plurality of functional groups; (7) As a coating treatment technical means, the universality is excellent, and the selection range of the object of coating and the raw material used for coating is wide.
The Plasma Enhanced Chemical Vapor Deposition (PECVD) process generates plasma through glow discharge, and the discharge method comprises microwave discharge, radio frequency discharge, ultraviolet and electric spark discharge and the like.
According to an embodiment of the invention, the preparation method comprises the following steps:
1) Substrate preparation
A cleaning process is required for the substrate before chemical vapor deposition is performed on the substrate. Dust, moisture, grease, or the like on the surface of the substrate may adversely affect the deposition effect. The substrate may be cleaned with acetone or isopropanol and then dried in a dry box.
2) Preparation of silane transition layer by chemical vapor deposition on substrate
(1) Placing a substrate in the reaction chamber of the reaction device, vacuumizing to 10-200 millitorr, and introducing auxiliary gas such as He, ar and O 2 Or a mixture of several gases.
(2) And introducing silane raw materials or monomer steam doped with a corrosion inhibitor into the reaction cavity, starting plasma discharge, and performing chemical vapor deposition to form the silane transition layer on the surface of the substrate.
3) Preparing a coating on the surface of the substrate provided with the silane transition layer to obtain a composite protective film layer
And (3) introducing first monomer steam and second monomer steam into the reaction cavity on the surface of the substrate on which the silane transition layer is prepared until the vacuum degree is 30-300 millitorr, starting plasma discharge, and performing chemical vapor deposition to form the composite protective film layer with the silane transition layer on the surface of the substrate.
4) Post-treatment
And closing the deposition plasma discharge, and introducing clean compressed air or inert gas to enable the reaction cavity of the reaction device to return to normal pressure. And then the substrate with the composite protective film layer is taken out from the reaction cavity.
According to an embodiment of the present invention, the step of preparing the silane transition layer and the step of preparing the composite film layer based on the silane transition layer respectively include two stages, one is a pretreatment stage, and the other is a coating stage (including a transition layer preparation and a coating preparation step), wherein in the pretreatment stage, the plasma discharge power is 120-500W, and the duration of discharge is 60-500 s. In the coating stage, the plasma discharge power is 10-180W, and the duration time is 400-7200 s. That is, in the pretreatment stage in the silane transition layer preparation step, the plasma discharge power is 120 to 500W, the duration of discharge is 60 to 500s, and in the coating stage in the silane transition layer preparation step, the plasma discharge power is 10 to 180W, and the duration of discharge is 400 to 7200s. In the step of preparing and forming the composite film layer on the basis of the silane transition layer, the plasma discharge power in the pretreatment stage is 120-500W, the continuous discharge time is 60-500 s, and in the step of preparing and forming the composite film layer on the basis of the silane transition layer, the plasma discharge power in the film plating stage is 10-180W, and the continuous discharge time is 400-7200 s.
According to embodiments of the present invention, the plasma discharge may be electrodeless discharge (e.g., rf inductively coupled discharge, microwave discharge), single electrode discharge (e.g., corona discharge, plasma jet formed by unipolar discharge), double electrode discharge (e.g., dielectric barrier discharge, bare electrode rf glow discharge), or multi-electrode discharge (e.g., discharge using floating electrode as the third electrode).
According to an embodiment of the present invention, in the substrate preparation step, a reaction chamber of the reaction apparatus forms the reaction chamber, and the reaction chamber may be a rotating body-shaped chamber or a cubic-shaped chamber, the volume of the reaction chamber is 50 to 1000L, the temperature of the reaction chamber is controlled to be 30 to 60 degrees celsius, and the flow rate of the inert gas is 5 to 300sccm.
According to an embodiment of the present invention, in the silane transition layer preparation step, the feeding mode of the gas may be one of single feeding, integral two feeding or three-way feeding, for example, when the gas is He, ar and O 2 In this case, the feeding can be performed by a three-way feeding method, such as Y-type three-way feeding.
According to an embodiment of the present invention, in the step of preparing the silane transition layer, the feeding manner of the first monomer and the second monomer may be performed through different feeding channels, for example, integrally feeding two monomers, so that the monomers reacting with each other are prevented from reacting in the conventional single-port feeding channel. The feeding of the silane raw material and the corrosion inhibitor can be carried out through different feeding channels, such as three-way feeding.
According to an embodiment of the present invention, in the step of preparing the silane transition layer, the corrosion inhibitor may be an organic corrosion inhibitor or an inorganic corrosion inhibitor or a mixture of an organic corrosion inhibitor and an inorganic corrosion inhibitor.
When the corrosion inhibitor is an organic corrosion inhibitor, the organic corrosion inhibitor is selected from the group consisting of: one or more of imidazoles and salts thereof, quinolines and salts thereof, pyrimidines and salts thereof, benzotriazole and derivatives thereof, organic amines and the like; the main components comprise: one or more of benzotriazole, benzimidazole, 2-thio-1-methylimidazole, dimercaptothiadiazole, 1-phenyl-4-methylimidazole, pyrazoline, tetrazole, uracil, 5-aminouracil, dithiouracil, N- (2-furfuryl) -p-toluidine, N- (5-methyl-2-furfuryl) -p-toluidine, hydroxyquinoline and the like.
When the corrosion inhibitor is an inorganic slow release agent, the inorganic corrosion inhibitor is selected from the group consisting of: lanthanum nitrate, cerium nitrate, molybdenum nitrate, erbium nitrate, zirconium nitrate, cobalt nitrate, yttrium nitrate, scandium nitrate, indium nitrate and other rare earth nitrate.
Further, the corrosion inhibitor may be dissolved in an organic solvent selected from the group consisting of: benzene and its derivatives such as water, formamide, trifluoroacetic acid, DMSO, acetonitrile, DMF, hexamethylphosphoramide, methanol, ethanol, acetic acid, isopropanol, isoamyl alcohol, divinylbenzene, and paraxylene.
According to an embodiment of the present invention, in the silane transition layer preparation step, the silane raw material may be a compound of the following formula Y-R-SiX 3 Wherein when the silane raw material is a hydrophilic silane, the hydrophilic silane Y is one of ureido groups, carboxylic acid, ether groups, amino groups, and the likeWherein when the silane raw material is hydrophobic silane, the hydrophobic silane Y is hydrocarbon group, thio group, ester group, phenyl group, epoxy group. R is one of C-C, C = C, C-N-C, C-S-C and the like. X is one or more of methoxy, ethoxy, chloro, bromo, acetoxy, amino and the like.
According to an embodiment of the present invention, when the silane raw material is a hydrophilic silane, the silane raw material may be selected from the group consisting of: one or more of ureidopropyltriethoxysilane, ureidopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, 2-aminoethyl-aminopropyltrimethoxysilane, diethylenetriaminopropyl trimethoxysilane, aminoethylaminopropyl methyldimethoxysilane and diethylenetriaminopropyl trimethoxysilane.
According to an embodiment of the present invention, when the silane raw material is a hydrophobic silane, the silane raw material may be selected from the group consisting of: phenyl triethoxysilane, vinyl propyl trimethoxysilane, vinyl triethoxysilane, vinyl trimethylsilane, 3-butenyltrimethylsilane, vinyl tributylketoximosilane, tetramethyl divinyl disiloxane, 1, 2-trifluoro vinyl triphenylsilane, hexaethyl cyclotrisiloxane, 3- (methacryloyloxy) propyl trimethoxysilane, phenyl tris (trimethylsiloxy) silane, diphenyl diethoxysilane, triphenyl chlorosilane, methyl vinyl dichlorosilane, trifluoropropyl trichlorosilane, trifluoropropyl methyldichlorosilane, dimethylphenyl chlorosilane, tributylchlorosilane, benzyl dimethylchlorosilane, hexamethylcyclotrisiloxane, octamethyl cyclotetrasiloxane, hexaphenyl cyclotrisiloxane, decamethyl cyclopentasiloxane, octaphenyl cyclotetrasiloxane, triphenylhydroxy silane, diphenyl dihydroxy silane, trifluoropropyl methyl cyclotrisiloxane, 2, 4-tetramethyl-6,6,8,8-tetraphenyl cyclotetrasiloxane, tetramethyl tetravinyl cyclotrisiloxane, 3-glycidoxy propyl triethoxy, tris- (trimethoxypropyl) silane, and tris- (trimethoxypropyl) siloxane.
According to the embodiment of the invention, in the preparation step of the silane transition layer, when the corrosion inhibitor comprises an organic corrosion inhibitor and/or an inorganic corrosion inhibitor, the mass part ratio of the organic corrosion inhibitor and/or the inorganic corrosion inhibitor to the corrosion inhibitor solution is 0-80 parts. The silane raw material can be composed of the following components in parts by mass: 0 to 100 parts of hydrophilic silane and 50 to 100 parts of hydrophobic silane.
According to an embodiment of the present invention, in the silane transition layer preparation step, the flow rate of the reaction raw material may be in the range of 10 to 1000ul/min.
According to an embodiment of the present invention, in the step of preparing the composite film layer based on the silane transition layer, the first monomer may be one or more of a low dipole moment organic monomer or a polyfunctional acrylate.
When the first monomer is a low dipole moment organic monomer, it may be selected from the group consisting of: para-xylene, benzene, toluene, carbon tetrafluoride, alpha-methylstyrene, poly-para-xylene, dimethylsiloxane, polydimethylsiloxanes of molecular weight 500-50000, allyl benzene, decafluorobiphenyl ketone, perfluoroallyl benzene, tetrafluoroethylene, hexafluoropropylene, 1H-perfluorooctylamine, perfluoroiodododecane, perfluorotributylamine, 1, 8-diiodoperfluorooctane, perfluorohexyl iodoane, perfluoroiodobutane, perfluoroiododecane, perfluorooctyl iodoane, 1, 4-bis (2 ',3' -epoxypropyl) perfluorobutane, dodecafluoro-2-methyl-2-pentene, 2- (perfluorobutyl) ethyl methacrylate, 2- (perfluorooctyl) ethyl iodide, perfluorodecyl ethyl iodide, 1, 2-tetrahydroperfluorohexyl iodide, perfluorobutyl ethylene, 1H, 2H-perfluoro-1-decene one or more of 2,4, 6-tris (perfluoroheptyl) -1,3, 5-triazine, perfluorohexyl ethylene, 3- (perfluoro-n-yl) -1, 2-epoxypropane, perfluorocyclic ether, perfluorododecyl ethylene, perfluorododecyl ethyl iodide, dibromo-p-xylene and 1, 4-tetraphenyl-1, 3-butadiene.
When the first monomer is a polyfunctional acrylate, it may be selected from the group consisting of: diethylene glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol dimethacrylate, pentafluorophenol acrylate, tripropylene glycol diacrylate, triethylene glycol dimethacrylate, dimethylaminoethyl methacrylate, allyl methacrylate, t-butyl methacrylate, glycidyl methacrylate, trimethylsilyl methacrylate, diethylene glycol dimethacrylate.
According to an embodiment of the present invention, in the step of preparing the composite film layer based on the silane transition layer, the second monomer may be a monofunctional fluorocarbons compound, and may be selected from the group consisting of: 3- (perfluoro-5-methyl hexyl) -2-hydroxypropyl methacrylate, 2- (perfluorodecyl) ethyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate, 2- (perfluorododecyl) ethyl acrylate, 2-perfluorooctyl ethyl acrylate, 1H, 2H-perfluorooctanol acrylate, 2- (perfluorobutyl) ethyl acrylate, (2H-perfluoropropyl) -2-acrylate, (perfluorocyclohexyl) methacrylate, 3-trifluoro-1-propyne, 1-ethynyl-3, 5-difluorobenzene or 4-ethynyl trifluorotoluene.
According to an embodiment of the present invention, in the step of preparing the composite film layer on the basis of the silane transition layer, the flow rate of the first monomer or the second monomer may range from 10 to 1000ul/min.
Example 1
In the preparation method of the coating taking the silane composite film as the self-repairing transition layer, the preparation method comprises the following steps:
(1) A circuit board (6 cm x 3 cm), a Fe sheet (30 x 20 x 2 mm), a Mg sheet (30 x 20 x 2 mm) were placed in a 500L plasma reaction apparatus, and a reaction chamber of the reaction apparatus was continuously evacuated to a vacuum degree of 200 mtorr and a chamber temperature of 30 ℃.
(2) And (3) introducing oxygen, wherein the flow is 120sccm, starting the radio frequency plasma discharge to pretreat the substrate, and continuously discharging for 60 seconds at the pretreatment stage, wherein the discharge power is 120W.
(3) 5% lanthanum nitrate (inorganic slow release agent) (isopropanol is dissolved (organic solvent)) and hexamethylcyclotrisiloxane (hydrophobic silane) and ureidopropyl trimethoxysilane (hydrophilic silane) (1:1) are simultaneously introduced into the Y-shaped tee joint, and chemical vapor deposition is carried out on the surface of the substrate to prepare the transition layer. The flow rates of the two monomers in the preparation process of the transition layer are 120 mu L/min and 120 mu L/min respectively, and the temperatures are respectively: the charging time is 3600s at 70 ℃ and 110 ℃, and the discharge power is 120w.
(4) After the preparation of the transition layer is finished, a tripropylene glycol diacrylate monomer (first monomer steam) is introduced into the single feed, the monomer flow is 480ul/min, the temperature is 110 ℃, the time is 3600s, and the discharge power is 35w; after the end, the 2- (perfluorodecyl) ethyl methacrylate monomer (second monomer steam) was again introduced at a flow rate of 120ul/min at a temperature of 75℃for 7200s and a discharge power of 150w.
(5) After the coating is prepared, air is introduced to restore the reaction cavity to normal pressure, and the circuit board, the Fe sheet and the Mg sheet with the composite protective film layer are taken out.
Example 2
In the preparation method of the coating taking the silane composite film as the self-repairing transition layer, the preparation method comprises the following steps:
(1) A circuit board (6 cm x 3 cm), a Fe sheet (30 x 20 x 2 mm), and a Mg sheet (30 x 20 x 2 mm) were placed in a 500L plasma reaction apparatus, and a reaction chamber of the reaction apparatus was continuously evacuated to a vacuum degree of 50 mtorr and a chamber temperature of 45 ℃.
(2) Argon is introduced, the flow is 5sccm, microwave discharge is started to pretreat the substrate, the discharge power in the pretreatment stage is 500W, and the discharge is continued for 200s.
(3) And 5% cerium nitrate (water-soluble) (inorganic corrosion inhibitor) and octamethyl cyclotetrasiloxane (hydrophobic silane) are simultaneously introduced into the Y-shaped tee joint, and chemical vapor deposition is carried out on the surface of the base material to prepare the transition layer. In the preparation process of the transition layer, the flow rates of the two monomers are 100 mu L/min and 100 mu L/min respectively, and the temperatures are respectively: the charging time is 3600s at 70 ℃ and 100 ℃, and the discharge power is 100w.
(4) After the preparation of the transition layer is finished, introducing diethylene glycol diacrylate monomer (first monomer), wherein the monomer flow is 1000ul/min, the temperature is 110 ℃, the time is 400s, and the discharge power is 50w; after the end, the 2- (perfluorodecyl) ethyl methacrylate monomer (second monomer) was again introduced at a flow rate of 160ul/min at a temperature of 75℃for 7200s and a discharge power of 180w.
(5) After the coating is prepared, air is introduced to restore the reaction cavity to normal pressure, and the circuit board, the Fe sheet and the Mg sheet with the composite protective film layer are taken out.
Example 3
In the preparation method of the coating taking the silane composite film as the self-repairing transition layer, the preparation method comprises the following steps:
(1) A circuit board (6 cm x 3 cm), a Fe sheet (30 x 20 x 2 mm), and a Mg sheet (30 x 20 x 2 mm) were placed in a 500L plasma reaction apparatus, and a reaction chamber of the reaction apparatus was continuously evacuated to a vacuum degree of 100 mtorr and a chamber temperature of 45 ℃.
(2) Helium is introduced, the flow is 120sccm, the radio frequency plasma discharge is started to pretreat the substrate, the discharge power in the pretreatment stage is 300W, and the discharge is continued for 90 seconds.
(3) A transition layer is prepared by simultaneously introducing 5% benzotriazole (organic slow-release agent) (divinylbenzene (organic solvent) for dissolution) and 2-aminoethyl-aminopropyl trimethoxysilane (hydrophilic silane) and thiopropyl trimethoxysilane (hydrophobic silane) (1:1) into a single feed, and performing chemical vapor deposition on the surface of a substrate. In the preparation process of the transition layer, the flow rates of the two monomers are 100 mu L/min and 100 mu L/min respectively, and the temperatures are respectively: the charging time is 3600s at 70 ℃ and 110 ℃, and the discharge power is 150w.
(4) After the preparation of the transition layer is finished, introducing a mixed monomer (1:1) of glycidyl methacrylate and diethylene glycol diacrylate, wherein the monomer flow is 520 mu L/min, the temperature is 110 ℃, the time is 3600s, and the discharge power is 25w; after the end, 2- (perfluorodecyl) ethyl methacrylate (second monomer) was again introduced at a flow rate of 160. Mu.L/min at a temperature of 75℃for 7200s and a discharge power of 180w.
(5) After the coating is prepared, air is introduced to restore the reaction cavity to normal pressure, and then the circuit board, the Fe sheet and the Mg sheet with the composite protective film layer are taken out.
Example 4
In the preparation method of the coating taking the silane film as the self-repairing transition layer, the preparation method comprises the following steps: :
(1) A circuit board (6 cm x 3 cm), a Fe sheet (30 x 20 x 2 mm), and a Mg sheet (30 x 20 x 2 mm) were placed in a 500L plasma reaction apparatus, and a reaction chamber of the reaction apparatus was continuously evacuated to a vacuum degree of 100 mtorr and a chamber temperature of 45 ℃.
(2) Helium is introduced, the flow is 120sccm, the radio frequency plasma discharge is started to pretreat the substrate, the discharge power in the pretreatment stage is 250W, and the discharge is continued for 100s.
(3) The transition layer is prepared by introducing 5% of dithiouracil (organic slow release agent) (DMF (organic solvent) for dissolution) and thiopropyl trimethoxysilane (hydrophobic silane) and 2-aminoethyl-aminopropyl trimethoxysilane (hydrophilic silane) (1:1) into the substrate through two feeding steps at the same time, and performing chemical vapor deposition on the surface of the substrate. In the preparation process of the transition layer, the flow rates of the two monomers are 150 mu L/min and 150 mu L/min respectively, and the temperatures are respectively: the charging time is 3600s at 100 ℃ and 110 ℃, and the discharge power is 150w.
(4) Introducing alpha-methyl styrene (the first monomer is a low dipole moment organic monomer) and diethylene glycol diacrylate (the first monomer is polyfunctional acrylic ester) mixed monomer (1:1), wherein the monomer flow is 520 mu L/min, the temperature is 110 ℃, the time is 3600s, and the discharge power is 25w; after the end, the (perfluorocyclohexyl) methacrylate (second monomer) was again introduced at a flow rate of 160. Mu.L/min at a temperature of 75℃for 7200s and a discharge power of 180w.
(5) After the coating is prepared, air is introduced to restore the reaction cavity to normal pressure, and the circuit board, the Fe sheet and the Mg sheet with the composite protective film layer are taken out.
Example 5
In the preparation method of the coating taking the silane film as the self-repairing transition layer, the preparation method comprises the following steps:
(1) A circuit board (6 cm x 3 cm), a Fe sheet (30 x 20 x 2 mm), a Mg sheet (30 x 20 x 2 mm) were placed in a 500L plasma reaction apparatus, and a reaction chamber of the reaction apparatus was continuously evacuated to a vacuum level of 10 mtorr and a chamber temperature of 60 ℃.
(2) Helium is introduced, the flow is 300sccm, the radio frequency plasma discharge is started to pretreat the substrate, the discharge power in the pretreatment stage is 150W, and the discharge is continued for 500s.
(3) And 5% dimercaptothiadiazole (dissolved in paraxylene), tetramethyl tetravinyl cyclotetrasiloxane (hydrophobic silane) and 2-aminoethyl-aminopropyl trimethoxy silane (hydrophilic silane) (1:1) are simultaneously introduced into the Y-shaped tee joint, and chemical vapor deposition is carried out on the surface of the substrate to prepare the transition layer. In the preparation process of the transition layer, the flow rates of the two monomers are 100 mu L/min and 100 mu L/min respectively, and the temperatures are respectively: 110 ℃ and 110 ℃, the charging time is 3600s, and the discharge power is 150w.
(4) After the preparation of the transition layer is finished, introducing mixed monomers (1:1) of glycidyl methacrylate and diethylene glycol diacrylate (polyfunctional acrylate of a first monomer), wherein the monomer flow is 520ul/min, the temperature is 110 ℃, the time is 3600s, and the discharge power is 25w; after the end, 2- (perfluorodecyl) ethyl methacrylate (second monomer) was again introduced at a flow rate of 160. Mu.L/min at a temperature of 75℃for 7200s and a discharge power of 180w.
Example 6
In the preparation method of the coating taking the silane composite film as the self-repairing transition layer, the preparation method comprises the following steps:
(1) A circuit board (6 cm x 3 cm), a Fe sheet (30 x 20 x 2 mm), and a Mg sheet (30 x 20 x 2 mm) were placed in a 500L plasma reaction apparatus, and a reaction chamber of the reaction apparatus was continuously evacuated to a vacuum degree of 100 mtorr and a chamber temperature of 45 ℃.
(2) Helium is introduced, the flow is 120sccm, the radio frequency plasma discharge is started to pretreat the substrate, the discharge power in the pretreatment stage is 300W, and the discharge is continued for 90 seconds.
(3) The transition layer was prepared by chemical vapor deposition on the substrate surface by single feed with simultaneous introduction of 2-aminoethyl-aminopropyl trimethoxysilane (hydrophilic silane) and thiopropyl trimethoxysilane (hydrophobic silane) (1:1). In the preparation process of the transition layer, the flow rates of the two monomers are 100 mu L/min and 100 mu L/min respectively, and the temperatures are respectively: the charging time is 3600s at 70 ℃ and 110 ℃, and the discharge power is 150w.
(4) After the preparation of the transition layer is finished, introducing a mixed monomer (1:1) of glycidyl methacrylate and diethylene glycol diacrylate, wherein the monomer flow is 520 mu L/min, the temperature is 110 ℃, the time is 3600s, and the discharge power is 25w; after the end, 2- (perfluorodecyl) ethyl methacrylate (second monomer) was again introduced at a flow rate of 160. Mu.L/min at a temperature of 75℃for 7200s and a discharge power of 180w.
(5) After the coating is prepared, air is introduced to restore the reaction cavity to normal pressure, and then the circuit board, the Fe sheet and the Mg sheet with the composite protective film layer are taken out.
Example 6 differs from example 3 in that no slow release agent was added in example 6.
Sweat test and salt spray resistance test were performed on the above examples, respectively, with specific test methods:
salt spray resistance test, and detection according to GB/T2423.18-2000 electrical and electronic product environment test method.
The test results are shown in the following table:
it can be seen that the composite protective film layer provided by the invention has better corrosion resistance, and particularly, the addition of the slow release agent is favorable for improving the corrosion resistance of the composite protective film layer, for example, the slow release agent is added in comparative example 3 and example 6, the slow release agent is not added in example 6, and the corrosion resistance of the composite protective film layer prepared in example 3 is obviously higher than that of the composite protective film layer prepared in example 6.
It will be appreciated by persons skilled in the art that the embodiments of the invention shown in the foregoing description are by way of example only and are not limiting. The objects of the present invention have been fully and effectively achieved. The functional and structural principles of the present invention have been shown and described in the examples and embodiments of the invention may be modified or practiced without departing from the principles described.
Claims (30)
1. The composite protective film layer with the silane transition layer is characterized by comprising the following components:
a silane transition layer, wherein the silane transition layer is formed mainly by organosilane through plasma chemical vapor deposition; and
a coating, wherein after forming the silane transition layer, the coating is formed on the silane transition layer by plasma chemical vapor deposition of a first monomer and a second monomer, respectively, in sequence, wherein the first monomer comprises one or two selected from the group consisting of a combination low-dipole moment organic monomer and an acrylic compound, wherein the second monomer comprises a fluorocarbonate compound, and the acrylic compound is selected from the group consisting of: one or more of diethylene glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol dimethacrylate, pentafluorophenol acrylate, tripropylene glycol diacrylate, triethylene glycol dimethacrylate, dimethylaminoethyl methacrylate, allyl methacrylate, t-butyl methacrylate, glycidyl methacrylate, trimethylsilyl methacrylate and diethylene glycol dimethacrylate;
Wherein the first monomer comprises the low dipole moment organic matter selected from the group consisting of: para-xylene, benzene, toluene, carbon tetrafluoride, alpha-methylstyrene, poly-para-xylene, allyl benzene, decafluorobiphenyl ketone, 1H-perfluorooctylamine, perfluoroiodododecane, perfluorotributylamine, 1, 8-diiodoperfluorooctane, perfluorohexyl iodoane, perfluoroiodobutane, perfluoroiododecane, perfluorooctyl iodoane, 1, 4-bis (2 ',3' -epoxypropyl) perfluorobutane, 2- (perfluorooctyl) iodoethane, perfluorodecyl ethyl iodide, 1, 2-tetrahydroperfluorohexyl iodide, 2,4, 6-tris (perfluoroheptyl) -1,3, 5-triazine, perfluorohexyl ethylene, perfluorocyclic ether, perfluorododecyl ethylene, perfluorododecyl ethyl iodide, dibromo-p-xylene and 1, 4-tetraphenyl-1, 3-butadiene;
wherein the structural formula of the organosilane is Y-R-SiX 3 Wherein Y is one of ureido, carboxylic acid, ether, amino, hydrocarbyl, thio, ester, phenyl, epoxy, wherein R is an organic carbon chain whichWherein X is selected from one of an oxygen-bearing group, a halogen group and a nitrogen-bearing group.
2. The composite protective film of claim 1, wherein the silane transition layer is deposited on a surface of a substrate.
3. The composite protective film layer according to claim 1, wherein the silane transition layer is formed from hydrophobic silane and/or hydrophilic silane by plasma chemical vapor deposition.
4. The composite protective film layer according to any one of claims 1 to 2, wherein the silane transition layer is formed from the organosilane and a corrosion inhibitor by plasma chemical vapor deposition, the corrosion inhibitor being an organic corrosion inhibitor, wherein the organic corrosion inhibitor is selected from the group consisting of: imidazole and its salt, quinoline and its salt, pyrimidine and its salt, benzotriazole and its derivative, and organic amine.
5. The composite protective film of claim 4, wherein the corrosion inhibitor is an organic corrosion inhibitor, wherein the organic corrosion inhibitor is selected from the group consisting of: one or more of benzotriazole, benzimidazole, 2-thio-1-methylimidazole, dimercaptothiadiazole, 1-phenyl-4-methylimidazole, pyrazoline, tetrazole, uracil, 5-aminouracil, dithiouracil, N- (2-furfuryl) -p-toluidine, N- (5-methyl-2-furfuryl) -p-toluidine and hydroxyquinoline.
6. The composite protective film of claim 4, wherein the corrosion inhibitor is an organic corrosion inhibitor and is selected from the group consisting of: one or more of benzotriazole, dithiouracil and dimercaptothiadiazole.
7. A composite protective film according to any one of claims 1 to 3, wherein the silane transition layer is formed from an organosilane and a corrosion inhibitor by plasma chemical vapour deposition, the corrosion inhibitor being an inorganic corrosion inhibitor, wherein the inorganic corrosion inhibitor is a rare earth nitrate.
8. The composite protective film layer of claim 7, wherein the inorganic corrosion inhibitor is selected from the group consisting of: lanthanum nitrate, cerium nitrate, molybdenum nitrate, erbium nitrate, zirconium nitrate, cobalt nitrate, yttrium nitrate, scandium nitrate and one or more of indium nitrate.
9. The composite protective film layer of claim 7, wherein the inorganic corrosion inhibitor is selected from the group consisting of: one or more of lanthanum nitrate and cerium nitrate.
10. The composite protective film of claim 1, wherein R is one of an organic carbon chain comprising C-C, C = C, C-N-C, C-S-C.
11. The composite protective film according to claim 1, wherein X is one of methoxy, ethoxy, chloro, bromo, acetoxy, amino.
12. The composite protective film layer of claim 1, wherein the organosilane comprises a hydrophilic silane and is selected from the group consisting of: one or more of ureidopropyl triethoxysilane, ureidopropyl trimethoxysilane, aminopropyl triethoxysilane, aminopropyl trimethoxysilane, 2-aminoethyl-aminopropyl trimethoxysilane, diethylenetriaminopropyl trimethoxysilane, aminoethylaminopropyl methyldimethoxy silane and diethylenetriaminopropyl trimethoxysilane.
13. The composite protective film layer of claim 1, wherein the organosilane is selected from the group consisting of: one or more of ureidopropyl trimethoxysilane and 2-aminoethyl-aminopropyl trimethoxysilane.
14. The composite protective film layer of claim 1, wherein the organosilane comprises a hydrophobic silane and is selected from the group consisting of: phenyl triethoxysilane, vinyl propyl trimethoxysilane, vinyl triethoxysilane, vinyl trimethylsilane, 3-butenyltrimethylsilane, vinyl tributylketoximosilane, tetramethyl divinyl disiloxane, 1, 2-trifluoro vinyl triphenylsilane, hexaethyl cyclotrisiloxane, 3- (methacryloyloxy) propyl trimethoxysilane, phenyl tris (trimethylsiloxy) silane, diphenyl diethoxysilane, triphenylchlorosilane, methyl vinyl dichlorosilane, trifluoropropyl trichlorosilane, trifluoropropyl methyldichlorosilane, dimethylphenyl chlorosilane, tributylchlorosilane, benzyl dimethylchlorosilane, hexamethylcyclotrisiloxane, octamethyl cyclotetrasiloxane, hexaphenyl cyclotrisiloxane, octaphenyl cyclotetrasiloxane, triphenylhydroxy silane, diphenyl dihydroxy silane, trifluoropropyl methyl cyclotrisiloxane, 2, 4-tetramethyl-6,6,8,8-tetraphenyl cyclotetrasiloxane, tetramethyl tetravinyl cyclotrisiloxane, 3-glycidoxy propyl triethoxy silane, gamma-trimethoxy-propyl trimethoxy silane, and gamma-glycidoxy-propyl silane.
15. The composite protective film layer of claim 1, wherein the organosilane is selected from the group consisting of: one or more of hexamethyl cyclotrisiloxane, octamethyl cyclotrisiloxane, tetramethyl tetravinyl cyclotrisiloxane and thiopropyl trimethoxy silane.
16. A composite protective film according to any one of claims 1 to 3, wherein the fluorocarbons are selected from the group consisting of: one or more of 3- (perfluoro-5-methyl hexyl) -2-hydroxypropyl methacrylate, 2- (perfluorodecyl) ethyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate, 2- (perfluorododecyl) ethyl acrylate, 2-perfluorooctyl ethyl acrylate, 1H, 2H-perfluorooctanol acrylate, 2- (perfluorobutyl) ethyl acrylate, (2H-perfluoropropyl) -2-acrylate or (perfluorocyclohexyl) methacrylate.
17. A coated product, characterized in that the product is coated with a composite protective film layer with a silane transition layer by plasma chemical vapor deposition, wherein organosilane forms the silane transition layer of the composite protective film layer on the surface of the product by plasma chemical vapor deposition, and then after the silane transition layer is formed, a coating layer is formed on the surface of the product coated with the silane transition layer by sequentially and respectively passing through plasma chemical vapor deposition by a first monomer and a second monomer to form the composite protective film layer, wherein the first monomer is one or two selected from the group consisting of a low dipole moment organic monomer and a multifunctional acrylate compound, and the second monomer is a fluorocarbonate compound;
Wherein the first monomer comprises the low dipole moment organic matter selected from the group consisting of: para-xylene, benzene, toluene, carbon tetrafluoride, alpha-methylstyrene, poly-para-xylene, allyl benzene, decafluorobiphenyl ketone, 1H-perfluorooctylamine, perfluoroiodododecane, perfluorotributylamine, 1, 8-diiodoperfluorooctane, perfluorohexyl iodoane, perfluoroiodobutane, perfluoroiododecane, perfluorooctyl iodoane, 1, 4-bis (2 ',3' -epoxypropyl) perfluorobutane, 2- (perfluorooctyl) iodoethane, perfluorodecyl ethyl iodide, 1, 2-tetrahydroperfluorohexyl iodide, 2,4, 6-tris (perfluoroheptyl) -1,3, 5-triazine, perfluorohexyl ethylene, perfluorocyclic ether, perfluorododecyl ethylene, perfluorododecyl ethyl iodide, dibromo-p-xylene and 1, 4-tetraphenyl-1, 3-butadiene;
wherein the structural formula of the organosilane is Y-R-SiX 3 Wherein Y is one of ureido, carboxylic acid, ether, amino, hydrocarbyl, thio, ester, phenyl, epoxy, wherein R is an organic carbon chain, and wherein X is one of an oxygen-bearing group, a halogen group, and a nitrogen-bearing group.
18. The coated product of claim 17, wherein the product is selected from the group consisting of: one or more of electronic products, silk fabrics, metal products, glass products, ceramic products.
19. The coated product of claim 17 or 18, wherein the silane transition layer is formed from a hydrophobic silane and/or a hydrophilic silane by plasma chemical vapor deposition.
20. The coated product of claim 17 or 18, wherein the silane transition layer is formed from the organosilane and a corrosion inhibitor by plasma chemical vapor deposition, the corrosion inhibitor being an organic corrosion inhibitor, wherein the organic corrosion inhibitor is selected from the group consisting of: imidazole and its salt, quinoline and its salt, pyrimidine and its salt, benzotriazole and its derivative, and organic amine.
21. The coated product of claim 17 or 18, wherein the silane transition layer is formed from the organosilane and a corrosion inhibitor by plasma chemical vapor deposition, the corrosion inhibitor being an inorganic corrosion inhibitor, wherein the inorganic corrosion inhibitor is a rare earth nitrate.
22. The preparation method of the composite protective film layer with the silane transition layer is characterized by comprising the following steps of:
forming a silane transition layer on the surface of a substrate by plasma chemical vapor deposition from organosilane; and
forming a coating layer by plasma chemical vapor deposition after the silane transition layer is formed so as to form a composite protective film layer with the silane transition layer;
In the step of depositing and forming the coating, respectively introducing first monomer and second monomer steam into a reaction cavity of a reaction device in sequence to form the coating in a plasma environment, wherein the first monomer is a low-dipole moment organic monomer and/or a polyfunctional acrylate compound, and the second monomer is a fluorocarbonate compound;
wherein the first monomer comprises the low dipole moment organic matter selected from the group consisting of: para-xylene, benzene, toluene, carbon tetrafluoride, alpha-methylstyrene, poly-para-xylene, allyl benzene, decafluorobiphenyl ketone, 1H-perfluorooctylamine, perfluoroiodododecane, perfluorotributylamine, 1, 8-diiodoperfluorooctane, perfluorohexyl iodoane, perfluoroiodobutane, perfluoroiododecane, perfluorooctyl iodoane, 1, 4-bis (2 ',3' -epoxypropyl) perfluorobutane, 2- (perfluorooctyl) iodoethane, perfluorodecyl ethyl iodide, 1, 2-tetrahydroperfluorohexyl iodide, 2,4, 6-tris (perfluoroheptyl) -1,3, 5-triazine, perfluorohexyl ethylene, perfluorocyclic ether, perfluorododecyl ethylene, perfluorododecyl ethyl iodide, dibromo-p-xylene and 1, 4-tetraphenyl-1, 3-butadiene;
Wherein the structural formula of the organosilane is Y-R-SiX 3 Wherein Y is one of ureido, carboxylic acid, ether, amino, hydrocarbyl, thio, ester, phenyl, epoxy, wherein R is an organic carbon chain, and wherein X is one of an oxygen-bearing group, a halogen group, and a nitrogen-bearing group.
23. The method of manufacturing of claim 22, wherein the depositing a silane transition layer step further comprises the steps of:
introducing auxiliary gas into a reaction cavity of a reaction device; and
and then introducing organosilane into the reaction cavity to form the silane transition layer on the surface of the substrate in a plasma environment.
24. The production method according to any one of claims 22 to 23, wherein in the above method, the deposition of the silane transition layer and the coating layer respectively includes a pretreatment stage in which a plasma discharge power is 120 to 500W for a discharge time of 60 to 500s and a plating stage in which a plasma discharge power is 10 to 180W for a discharge time of 400 to 7200s.
25. The production method according to any one of claims 22 to 23, wherein in the above method, the plasma discharge is an electrodeless discharge, a single electrode discharge, a double electrode discharge, or a multi-electrode discharge.
26. The production method according to any one of claims 22 to 23, wherein in the above method, the silane transition layer is produced starting from an organosilane and a corrosion inhibitor solution.
27. The production method according to claim 22, wherein in the above method, the organosilane comprises a hydrophilic silane and a hydrophobic silane in a mass ratio of 0 to 100 parts and 50 to 100 parts.
28. The process of claim 22 wherein in said process, the mutually reactive starting materials are introduced into said reaction chamber through different channels.
29. The method of manufacture of claim 26, wherein the corrosion inhibitor is an organic corrosion inhibitor, wherein the organic corrosion inhibitor is selected from the group consisting of: imidazole and its salt, quinoline and its salt, pyrimidine and its salt, benzotriazole and its derivative, and organic amine.
30. The method of making according to claim 26, wherein the corrosion inhibitor is an inorganic corrosion inhibitor, wherein the inorganic corrosion inhibitor is a rare earth nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010342097.XA CN111570216B (en) | 2020-04-27 | 2020-04-27 | Composite protective film layer with silane transition layer, preparation method thereof and product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010342097.XA CN111570216B (en) | 2020-04-27 | 2020-04-27 | Composite protective film layer with silane transition layer, preparation method thereof and product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111570216A CN111570216A (en) | 2020-08-25 |
| CN111570216B true CN111570216B (en) | 2023-10-13 |
Family
ID=72122748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010342097.XA Active CN111570216B (en) | 2020-04-27 | 2020-04-27 | Composite protective film layer with silane transition layer, preparation method thereof and product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111570216B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115400930A (en) * | 2021-05-26 | 2022-11-29 | 江苏菲沃泰纳米科技股份有限公司 | Plasma polymerization coating, preparation method and device |
| CN115505907A (en) * | 2021-06-22 | 2022-12-23 | 江苏菲沃泰纳米科技股份有限公司 | Composite film applied to flexible substrate and preparation method and product thereof |
| WO2023011270A1 (en) * | 2021-08-05 | 2023-02-09 | 江苏菲沃泰纳米科技股份有限公司 | Polymer film layer, preparation method therefor, and led product |
| CN113773682B (en) * | 2021-08-25 | 2022-10-11 | 佛山市思博睿科技有限公司 | Hydrophobic material for low-temperature plasma chemical vapor deposition and method for preparing nano-film by using same |
| CN115991951B (en) * | 2021-10-20 | 2024-02-20 | 江苏菲沃泰纳米科技股份有限公司 | Composite coating, preparation method and device |
| CN116558327A (en) * | 2022-01-27 | 2023-08-08 | 浙江三花智能控制股份有限公司 | Heat exchanger and composite material for heat exchanger |
| CN114950900A (en) * | 2022-04-22 | 2022-08-30 | 上海酷聚科技有限公司 | Preparation method of organic film, organic film structure and deposition equipment |
| CN115354309B (en) * | 2022-07-29 | 2023-10-31 | 四川中测标物科技有限公司 | Method for treating inner surface of aluminum alloy gas cylinder and aluminum alloy gas cylinder |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7045170B1 (en) * | 2002-04-03 | 2006-05-16 | Sandia Corporation | Anti-stiction coating for microelectromechanical devices |
| CN107587120A (en) * | 2017-08-23 | 2018-01-16 | 无锡荣坚五金工具有限公司 | A kind of preparation method of the high insulating nano protective coating with modulated structure |
| CN107587119A (en) * | 2017-08-23 | 2018-01-16 | 无锡荣坚五金工具有限公司 | A kind of preparation method of the high insulating rigid nano protecting coating of composite construction |
| CN107686986A (en) * | 2017-08-23 | 2018-02-13 | 江苏菲沃泰纳米科技有限公司 | A kind of preparation method of the organic silicon nano protective coating of modulated structure |
| CN107699868A (en) * | 2017-08-23 | 2018-02-16 | 江苏菲沃泰纳米科技有限公司 | A kind of preparation method of high-insulativity nano protecting coating |
| KR20180067275A (en) * | 2016-12-12 | 2018-06-20 | 한국과학기술원 | Method of Preparing Insulator Thin Film for Organic Thin-film Transistor |
| CN108425104A (en) * | 2018-03-12 | 2018-08-21 | 江苏菲沃泰纳米科技有限公司 | A kind of coating production using sulfhydryl compound as transition zone |
| EP3446793A1 (en) * | 2017-08-23 | 2019-02-27 | Molecular Plasma Group SA | Soft plasma polymerization process for a mechanically durable superhydrophobic nanostructured coating |
| CN109402611A (en) * | 2018-10-24 | 2019-03-01 | 江苏菲沃泰纳米科技有限公司 | A kind of silicon-containing copolymer nano coating and preparation method thereof |
| TW202003911A (en) * | 2018-05-04 | 2020-01-16 | 美商菲沃泰科技公司 | Nano-coating protection method for electrical connectors |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10351729B2 (en) * | 2016-03-03 | 2019-07-16 | Motorola Mobility Llc | Polysiloxane films and methods of making polysiloxane films |
-
2020
- 2020-04-27 CN CN202010342097.XA patent/CN111570216B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7045170B1 (en) * | 2002-04-03 | 2006-05-16 | Sandia Corporation | Anti-stiction coating for microelectromechanical devices |
| KR20180067275A (en) * | 2016-12-12 | 2018-06-20 | 한국과학기술원 | Method of Preparing Insulator Thin Film for Organic Thin-film Transistor |
| CN107587120A (en) * | 2017-08-23 | 2018-01-16 | 无锡荣坚五金工具有限公司 | A kind of preparation method of the high insulating nano protective coating with modulated structure |
| CN107587119A (en) * | 2017-08-23 | 2018-01-16 | 无锡荣坚五金工具有限公司 | A kind of preparation method of the high insulating rigid nano protecting coating of composite construction |
| CN107686986A (en) * | 2017-08-23 | 2018-02-13 | 江苏菲沃泰纳米科技有限公司 | A kind of preparation method of the organic silicon nano protective coating of modulated structure |
| CN107699868A (en) * | 2017-08-23 | 2018-02-16 | 江苏菲沃泰纳米科技有限公司 | A kind of preparation method of high-insulativity nano protecting coating |
| EP3446793A1 (en) * | 2017-08-23 | 2019-02-27 | Molecular Plasma Group SA | Soft plasma polymerization process for a mechanically durable superhydrophobic nanostructured coating |
| CN108425104A (en) * | 2018-03-12 | 2018-08-21 | 江苏菲沃泰纳米科技有限公司 | A kind of coating production using sulfhydryl compound as transition zone |
| TW202003911A (en) * | 2018-05-04 | 2020-01-16 | 美商菲沃泰科技公司 | Nano-coating protection method for electrical connectors |
| CN109402611A (en) * | 2018-10-24 | 2019-03-01 | 江苏菲沃泰纳米科技有限公司 | A kind of silicon-containing copolymer nano coating and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李砚咸.5.偶联剂.《涂料模具》.中国原子能出版社,2019,第126页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111570216A (en) | 2020-08-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111570216B (en) | Composite protective film layer with silane transition layer, preparation method thereof and product | |
| JP5297652B2 (en) | Method and apparatus for coating a substrate using dielectric barrier discharge | |
| EP1787796A1 (en) | Gas barrier multilayer film and method for producing same | |
| JP6056854B2 (en) | GAS BARRIER FILM, METHOD FOR PRODUCING GAS BARRIER FILM, AND ELECTRONIC DEVICE | |
| CN104982091B (en) | Organic electroluminescent device and lighting device | |
| JP6122116B2 (en) | BARRIER FILM COATING AND ITS MANUFACTURING AND USING METHOD | |
| WO2012106184A2 (en) | Vapor-deposited coating for barrier films and methods of making and using the same | |
| US10804419B2 (en) | Photovoltaic devices with encapsulating barrier film | |
| JP2011524077A5 (en) | ||
| KR20130032370A (en) | Gas barrier film, process for production of gas barrier film, and electronic device | |
| CN115551955B (en) | Fluorinated coupling agent and fluorinated (co) polymer layer prepared using the same | |
| JPH0848543A (en) | Plasma-strengthened chemical vapor deposition of anticlouding and scratch-resistant coating on varions substrates | |
| KR20070072899A (en) | Improved deposition rate plasma enhanced chemical vapor process | |
| KR20130086381A (en) | Gas-barrier film and electronic device | |
| TW201536887A (en) | Junction-functionalized block copolymers | |
| JP2013082106A (en) | Gas barrier laminate | |
| JP4107411B2 (en) | Laminated body and method for producing the same | |
| TW200827469A (en) | Improved plasma-enhanced chemical vapor deposition coating process | |
| JP2003342731A (en) | Laminate and manufacturing method | |
| JP4835031B2 (en) | Method for producing gas barrier film, method for producing organic electroluminescence resin substrate, and method for producing organic electroluminescence element | |
| TWI827055B (en) | Plasma polymerization coating, preparation method and device | |
| JP2022505770A (en) | Barrier film | |
| WO2018207508A1 (en) | Gas barrier film and method for producing gas barrier film | |
| JP3197007B2 (en) | Silicon polymer insulating film on semiconductor substrate and method for forming the film | |
| CN109890607A (en) | Gas barrier film and device comprising it |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: No.108, Xixian Road, Meicun street, Xinwu District, Wuxi City, Jiangsu Province, 214000 Applicant after: Jiangsu feiwotai nanotechnology Co.,Ltd. Address before: No. 108, Xixian Road, Meicun street, Xinwu District, Wuxi City, Jiangsu Province, 214112 Applicant before: Jiangsu Favored Nanotechnology Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: No.182, East Ring Road, Yuqi supporting area, Huishan Economic Development Zone, Wuxi City, Jiangsu Province, 214000 Applicant after: Jiangsu feiwotai nanotechnology Co.,Ltd. Address before: No.108, Xixian Road, Meicun street, Xinwu District, Wuxi City, Jiangsu Province, 214000 Applicant before: Jiangsu feiwotai nanotechnology Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |