阅读说明：本技术 具有硅烷过渡层的复合防护膜层及其制备方法和产品 (Composite protective film layer with silane transition layer and preparation method and product thereof ) 是由 宗坚 蔡泉源 蒋金海 于 2020-04-27 设计创作，主要内容包括：具有硅烷过渡层的复合防护膜层及其制备方法和产品,其中所述具有硅烷过渡层的复合防护膜层包括一硅烷过渡层和一涂层,其中所述硅烷过渡层是由有机硅烷通过等离子化学气相沉积形成,其中在形成所述硅烷过渡层之后,所述涂层由第一单体和第二单体通过等离子化学气相沉积在所述硅烷过渡层形成,其中所述第一单体是选自低偶极矩有机物单体和多官能度丙烯酸酯类化合物中的一种或两种,其中所述第二单体是氟碳酸酯类化合物。(The composite protective film layer with the silane transition layer comprises the silane transition layer and a coating layer, wherein the silane transition layer is formed by organosilane through plasma chemical vapor deposition, after the silane transition layer is formed, the coating layer is formed by a first monomer and a 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 fluorocarbon ester compounds.)

1. Composite protective film layer with silane transition layer, characterized in that includes:

a silane transition layer, wherein the silane transition layer is formed by plasma chemical vapor deposition of organosilane; and

a coating, wherein after forming the silane transition layer, the coating is formed by plasma chemical vapor deposition of a first monomer and a second monomer onto the silane transition layer, wherein the first monomer comprises one or two selected from a combination low dipole moment organic monomer and a multifunctional acrylate compound, and wherein the second monomer comprises a fluorocarbon ester compound.

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 of claim 1 wherein the silane transition layer is formed from a hydrophobic silane and/or a hydrophilic silane by plasma chemical vapor deposition.

4. The composite protective film layer of any of claims 1 to 3 wherein the silane transition layer is formed by plasma chemical vapor deposition of the organosilane and a corrosion inhibitor, 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 layer of claim 4 wherein the corrosion inhibitor is an organic corrosion inhibitor, wherein the organic corrosion inhibitor is selected from the group consisting of: benzotriazole, benzimidazole, 2-sulfenyl-1-methylimidazole, dimercapto thiadiazole, 1-phenyl-4-methylimidazole, pyrazoline, tetrazole, uracil, 5-amino uracil, dithiouracil, N- (2-furfuryl) -p-toluidine, N- (5-methyl-2-furfuryl) -p-toluidine and hydroxyquinoline.

6. The composite protective film layer of claim 4 wherein the slow release agent is an organic slow release agent and is selected from the group consisting of combinations of: one or more of benzotriazole, dithiouracil and dimercapto thiadiazole.

7. The composite protective film layer of any of claims 1 to 3 wherein the silane transition layer is formed by plasma chemical vapor deposition of an organosilane and a corrosion inhibitor, 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 combinations 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 slow release agent is selected from the group consisting of: one or more of lanthanum nitrate and cerium nitrate.

10. The composite protective film layer of any of claims 1 to 3 wherein the organosilane has the formula Y-R-SiX₃Wherein Y is one of carbamido, carboxylic acid, ether group, amino group, alkyl group, sulfur group, ester group, phenyl group and epoxy group, wherein R is organic carbon chain, and X is one of oxygen group, halogen group and nitrogen group.

11. The composite barrier film layer of claim 10, wherein R is one of organic carbon chains including C-C, C ═ C, C-N-C, C-S-C.

12. The composite protective film layer of claim 10 wherein X is one of methoxy, ethoxy, chloro, bromo, acetoxy, amino.

13. The composite protective film layer of claim 10 wherein the organosilane comprises a hydrophilic silane and is selected from the group consisting of: one or more of ureidopropyltriethoxysilane, ureidopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, 2-aminoethyl-aminopropyltrimethoxysilane, diethylenetriaminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane and diethylenetriaminopropyltrimethoxysilane.

14. The composite protective film layer of claim 10 wherein the organosilane is selected from the group consisting of combinations of: one or more of ureidopropyltrimethoxysilane and 2-aminoethyl-aminopropyltrimethoxysilane.

15. The composite protective film layer of claim 10 wherein the organosilane comprises a hydrophobic silane and is selected from the group consisting of: phenyltriethoxysilane, vinylpropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethylsilane, 3-butenyltrimethylsilane, vinyltributketoximosilane, tetramethyldivinyldisiloxane, 1,2, 2-trifluorovinyltriphenylsilane, hexaethylcyclotrisiloxane, 3- (methacryloyloxy) propyltrimethoxysilane, phenyltris (trimethylsiloxy) silane, diphenyldiethoxysilane, triphenylchlorosilane, methylvinyldichlorosilane, trifluoropropyltrichlorosilane, trifluoropropylmethyldichlorosilane, dimethylphenylchlorosilane, tributylchlorosilane, benzyldimethylchlorosilane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, hexaphenylcyclotrisiloxane, decamethylcyclopentasiloxane, octaphenylcyclotetrasiloxane, triphenylhydroxysilane, vinyltrimethylsilane, one or more of diphenyl dihydroxy silane, trifluoropropylmethyl cyclotrisiloxane, 2,4, 4-tetramethyl-6, 6,8, 8-tetraphenyl cyclotetrasiloxane, tetramethyl tetravinylcyclotetrasiloxane, 3-glycidoxypropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, decamethylcyclopentasiloxane, thiopropyltrimethoxysilane and bis- [ gamma- (triethoxysilyl) propyl ] -tetrasulfide.

16. The composite protective film layer of claim 10 wherein the organosilane is selected from the group consisting of combinations of: one or more of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane and thiopropyltrimethoxysilane.

17. The composite protective film layer of any of claims 1 to 3 wherein the first monomer comprises the low-dipole moment organic selected from the group consisting of: p-xylene, benzene, toluene, carbon tetrafluoride, alpha-methylstyrene, poly-p-dichlorotoluene, dimethylsiloxane, 500-molecule-containing 50000 polydimethylsiloxane, allylbenzene, decafluorobiphenyl ketone, perfluoroallylbenzene, tetrafluoroethylene, hexafluoropropylene, 1H-perfluorooctylamine, perfluoroiodododecane, perfluorotributylamine, 1, 8-diiodoperfluorooctane, perfluorohexyliodoalkane, perfluoroiodobutane, perfluoroiododecane, perfluorooctyliodoalkane, 1, 4-bis (2 ',3' -epoxypropyl) perfluorobutane, dodecafluoro-2-methyl-2-pentene, 2- (perfluorobutyl) ethyl methacrylate, 2- (perfluorooctyl) iodoethane, One or more of perfluorodecylethyl iodide, 1,2, 2-tetrahydroperfluorohexyl iodide, perfluorobutylethylene, 1H, 2H-perfluoro-1-decene, 2,4, 6-tris (perfluoroheptyl) -1,3, 5-triazine, perfluorohexylethylene, 3- (perfluoro-n-yl) -1, 2-epoxypropane, perfluorocyclic ether, perfluorododecylethylene, perfluorododecylethyl iodide, dibromo-p-xylene and 1,1,4, 4-tetraphenyl-1, 3-butadiene.

18. The composite protective film layer of any of claims 1 to 3 wherein the first monomer comprises the multifunctional acrylate compound 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, tert-butyl methacrylate, glycidyl methacrylate, trimethylsilyl methacrylate and diethylene glycol dimethacrylate.

19. A composite protective film layer according to any one of claims 1 to 3 wherein the fluorocarbon ester based compound is selected from the group consisting of: 3- (perfluoro-5-methyl hexyl) -2-hydroxypropyl methacrylate, 2- (perfluoro decyl) ethyl methacrylate, 2- (perfluoro hexyl) ethyl methacrylate, 2- (perfluoro dodecyl) ethyl acrylate, 2-perfluoro octyl ethyl acrylate, 1H,2H, 2H-perfluoro octanol acrylate, 2- (perfluoro butyl) ethyl acrylate, (2H-perfluoro propyl) -2-acrylate, (perfluoro cyclohexyl) methacrylate, 3,3, 3-trifluoro-1-propyne, 1-ethynyl-3, 5-difluorobenzene or 4-ethynyl trifluorotoluene.

20. A coated product characterized in that the product is coated with a composite protective film layer having a silane transition layer by plasma chemical vapor deposition, wherein organosilane is formed on the surface of the product by plasma chemical vapor deposition to form the silane transition layer of the composite protective film layer, 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 two selected from a combination of a low dipole moment organic monomer and a polyfunctional acrylate compound, wherein the second monomer is a fluorocarbon ester compound.

21. The coated product according to claim 20, wherein the product is selected from one or more of a combination electronic product, a silk fabric, a metal product, a glass product, a ceramic product.

22. The coated product according to claim 20 or 21, wherein the silane transition layer is formed from hydrophobic silane and/or hydrophilic silane by plasma chemical vapour deposition.

23. The coated product according to claim 20 or 21, wherein the organosilane has the formula Y-R-SiX₃Wherein Y is one of carbamido, carboxylic acid, ether group, amino group, alkyl group, sulfur group, ester group, phenyl group and epoxy group, wherein R is organic carbon chain, and X is one of oxygen group, halogen group and nitrogen group.

24. The coated product according to claim 20 or 21, wherein the silane transition layer is formed by plasma chemical vapour deposition of the organosilane and a corrosion inhibitor, 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.

25. The coated product according to claim 20 or 21, wherein the silane transition layer is formed by plasma chemical vapour deposition of the organosilane and a slow release agent, the slow release agent being an inorganic slow release agent, wherein the inorganic corrosion inhibitor is a rare earth nitrate.

26. The preparation method of the composite protective film layer with the silane transition layer is characterized by comprising the following steps:

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 together with the silane transition layer.

27. The method of claim 26, wherein the step of depositing a silane transition layer further comprises the steps of:

introducing auxiliary gas into a reaction cavity of a reaction device; and

then introducing organosilane into the reaction cavity to form the silane transition layer on the surface of the substrate in a plasma environment.

28. The method according to claim 27, wherein in the step of 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 under 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 fluorocarbon ester compound.

29. The method according to any one of claims 26 to 28, wherein in the method, the deposition of the silane transition layer and the coating layer comprises a pretreatment stage in which a plasma discharge power is 120 to 500W and a discharge duration is 60 to 500s and a coating stage in which a plasma discharge power is 10 to 180W and a discharge duration is 400 to 7200s, respectively.

30. The production method according to any one of claims 26 to 28, wherein in the above method, the plasma discharge mode is an electrodeless discharge, a single-electrode discharge, a double-electrode discharge or a multiple-electrode discharge.

31. The production method according to any one of claims 26 to 28, wherein in the above method, the silane transition layer is produced using an organosilane and a resist solution as raw materials.

32. The production method according to claim 27 or 28, wherein in the above method, the organosilane includes 0 to 100 parts by mass of a hydrophilic silane and 50 to 100 parts by mass of a hydrophobic silane.

33. The method of claim 27 or 28, wherein the organosilane has the formula Y-R-SiX₃Wherein Y is one of carbamido, carboxylic acid, ether group, amino group, alkyl group, sulfur group, ester group, phenyl group and epoxy group, wherein R is organic carbon chain, and X is one of oxygen group, halogen group and nitrogen group.

34. The method as claimed in claim 28, wherein in the above method, mutually reactive raw materials are introduced into the reaction chamber through different passages.

35. The method of claim 31, wherein the corrosion inhibitor is an organic corrosion inhibitor, wherein the organic corrosion inhibitor is selected from the group consisting of combinations of: imidazole and its salt, quinoline and its salt, pyrimidine and its salt, benzotriazole and its derivative, and organic amine.

36. The preparation method according to claim 31, wherein the slow-release agent is an inorganic slow-release agent, wherein the inorganic corrosion inhibitor is a rare earth nitrate.

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 proofings, namely mold, moisture and salt spray, are issues that require great attention in the storage, transportation and use of electronic equipment. Once the safeguards are not in place, the electronic device may fail because any of these problems cause a short circuit.

At present, the protection of electronic products by adopting a protective film layer is an effective measure for dealing with three-prevention problems. The protective film is prepared on the surface of the electronic product by a specific method, and there are generally two 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 certain damage to electronic products. The thickness of the film layer prepared by the liquid phase preparation method is mostly dozens of microns, which influences the heat dissipation and signal transmission of electronic products.

The most typical application in the latter method is the evaporation of parylene coatings, which are polymers of p-xylene. In this manner, p-xylene is first heated to 680 degrees Celsius to form active p-xylene dimers, and then the temperature is reduced to enable the polymer to be deposited on the surface of the electronic product to form a polymer coating. However, parylene needs to be deposited under vacuum conditions for preparation, that is, conditions for coating preparation require high temperature and high vacuum. In addition, similar to the liquid phase method, the thickness of the evaporated parylene coating needs to be dozens of microns, and if the thickness of the film is smaller, the protective performance of the film on electronic products is affected.

Furthermore, the film layer is prepared by adopting a liquid phase preparation method or a method of evaporating a parylene coating, the selectivity of the film layer to raw material monomers is poor, and most of the prepared film layer is a single film layer and is difficult to meet the protection requirements of electronic products under different environments.

Disclosure of Invention

One advantage of the present invention is to provide a composite protective film with a silane transition layer, and a preparation method and a product thereof, wherein the composite protective film has low requirements for preparation conditions, and is suitable for popularization and application.

Another advantage of the present invention is to provide a composite protective film with a silane transition layer, a method for preparing the same, and a product thereof, wherein the composite protective film can be prepared to be thinner, for example, nanometer-sized, and still provide better protective performance when the composite protective film is thinner.

Another advantage of the present invention is to provide a composite protective film with a silane transition layer, a method for preparing the same, and a product thereof, wherein the composite protective film is prepared by using a plasma chemical vapor deposition method, and can be applied to a plurality of raw material monomers.

Another advantage of the present invention is to provide a composite protective film with a silane transition layer, a method for preparing the same, and a product thereof, wherein the composite protective film is prepared by using a plasma chemical vapor deposition method, has a low preparation temperature, is suitable for preparing various types of electronic devices, and does not damage the electronic devices during the preparation process.

Another advantage of the present invention is to provide a composite protective film layer having a silane transition layer, a method for preparing the same, and a product thereof, wherein the composite protective film layer includes a silane transition layer and a coating layer, and wherein the silane transition layer can improve the 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, which can improve the corrosion resistance of the composite protective film, a method for preparing the same, and a product thereof.

Another advantage of the present invention is to provide a composite protective film having a silane transition layer, and a method for preparing the same, and a product thereof, wherein the composite protective film is cross-linked to form a dense network structure by introducing a multifunctional group to form a plurality of active sites in a plasma discharge environment, so as to improve corrosion resistance and stability.

Another advantage of the present invention is to provide a composite protective film of a silane transition layer, a method for preparing the same, and a product thereof, wherein the method for preparing the same reduces the phenomenon that raw material monomers react with each other in a single channel in the conventional preparation method by means of multi-channel feeding.

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 of organosilane; and

a coating layer, wherein after the silane transition layer is formed, the coating layer 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 the second monomer is a fluorocarbon ester 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 invention, the silane transition layer is formed by plasma chemical vapor deposition of hydrophobic silane and/or hydrophilic silane.

According to at least one embodiment of the invention, the silane transition layer is formed by plasma chemical vapor deposition of organosilane and corrosion inhibitor, the corrosion inhibitor is organic corrosion inhibitor, wherein the organic corrosion inhibitor is selected from one or more of imidazole and its salt, quinoline and its salt, pyrimidine and its salt, benzotriazole and its derivative, and organic amine. 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 the combinations: benzotriazole, benzimidazole, 2-sulfenyl-1-methylimidazole, dimercapto thiadiazole, 1-phenyl-4-methylimidazole, pyrazoline, tetrazole, uracil, 5-amino uracil, 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 sustained release agent is an organic sustained release agent and is selected from the group consisting of combinations of: one or more of benzotriazole, dithiouracil and dimercapto thiadiazole.

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 invention, the organosilane has the formula Y-R-SiX₃Wherein Y is one of carbamido, carboxylic acid, ether group, amino group, alkyl group, sulfur group, ester group, phenyl group and epoxy group, wherein R is organic carbon chain, and X is one of oxygen group, halogen group and nitrogen 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 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 ureidopropyltriethoxysilane, ureidopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, 2-aminoethyl-aminopropyltrimethoxysilane, diethylenetriaminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane and diethylenetriaminopropyltrimethoxysilane.

According to at least one embodiment of the invention, the organosilane is selected from the group consisting of: one or more of ureidopropyltrimethoxysilane and 2-aminoethyl-aminopropyltrimethoxysilane.

According to at least one embodiment of the invention, the organosilane comprises a hydrophobic silane and is selected from the group consisting of: phenyltriethoxysilane, vinylpropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethylsilane, 3-butenyltrimethylsilane, vinyltributketoximosilane, tetramethyldivinyldisiloxane, 1,2, 2-trifluorovinyltriphenylsilane, hexaethylcyclotrisiloxane, 3- (methacryloyloxy) propyltrimethoxysilane, phenyltris (trimethylsiloxy) silane, diphenyldiethoxysilane, triphenylchlorosilane, methylvinyldichlorosilane, trifluoropropyltrichlorosilane, trifluoropropylmethyldichlorosilane, dimethylphenylchlorosilane, tributylchlorosilane, benzyldimethylchlorosilane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, hexaphenylcyclotrisiloxane, decamethylcyclopentasiloxane, octaphenylcyclotetrasiloxane, triphenylhydroxysilane, vinyltrimethylsilane, one or more of diphenyl dihydroxy silane, trifluoropropylmethyl cyclotrisiloxane, 2,4, 4-tetramethyl-6, 6,8, 8-tetraphenyl cyclotetrasiloxane, tetramethyl tetravinylcyclotetrasiloxane, 3-glycidoxypropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, decamethylcyclopentasiloxane, thiopropyltrimethoxysilane and bis- [ gamma- (triethoxysilyl) propyl ] -tetrasulfide.

According to at least one embodiment of the invention, the organosilane is selected from the group consisting of: one or more of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane and thiopropyltrimethoxysilane.

According to at least one embodiment of the present invention, the first monomer comprises a low-dipole moment organic selected from the group consisting of: p-xylene, benzene, toluene, carbon tetrafluoride, alpha-methylstyrene, poly-p-dichlorotoluene, dimethylsiloxane, 500-molecule-containing 50000 polydimethylsiloxane, allylbenzene, decafluorobiphenyl ketone, perfluoroallylbenzene, tetrafluoroethylene, hexafluoropropylene, 1H-perfluorooctylamine, perfluoroiodododecane, perfluorotributylamine, 1, 8-diiodoperfluorooctane, perfluorohexyliodoalkane, perfluoroiodobutane, perfluoroiododecane, perfluorooctyliodoalkane, 1, 4-bis (2 ',3' -epoxypropyl) perfluorobutane, dodecafluoro-2-methyl-2-pentene, 2- (perfluorobutyl) ethyl methacrylate, 2- (perfluorooctyl) iodoethane, One or more of perfluorodecylethyl iodide, 1,2, 2-tetrahydroperfluorohexyl iodide, perfluorobutylethylene, 1H, 2H-perfluoro-1-decene, 2,4, 6-tris (perfluoroheptyl) -1,3, 5-triazine, perfluorohexylethylene, 3- (perfluoro-n-yl) -1, 2-epoxypropane, perfluorocyclic ether, perfluorododecylethylene, perfluorododecylethyl iodide, dibromo-p-xylene and 1,1,4, 4-tetraphenyl-1, 3-butadiene.

According to at least one embodiment of the invention, the first monomer comprises a multifunctional acrylate compound 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, tert-butyl methacrylate, glycidyl methacrylate, trimethylsilyl methacrylate and diethylene glycol dimethacrylate.

According to at least one embodiment of the invention, the second monomer comprises a fluorocarbon-based compound selected from the group consisting of: 3- (perfluoro-5-methyl hexyl) -2-hydroxypropyl methacrylate, 2- (perfluoro decyl) ethyl methacrylate, 2- (perfluoro hexyl) ethyl methacrylate, 2- (perfluoro dodecyl) ethyl acrylate, 2-perfluoro octyl ethyl acrylate, 1H,2H, 2H-perfluoro octanol acrylate, 2- (perfluoro butyl) ethyl acrylate, (2H-perfluoro propyl) -2-acrylate, (perfluoro cyclohexyl) methacrylate, 3,3, 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 a product is coated with a composite protective film having a silane transition layer by plasma chemical vapor deposition, wherein an organic silane is formed on a surface of the product by plasma chemical vapor deposition to form the silane transition layer of the composite protective film, 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, wherein the first monomer is one or both of a low dipole moment organic monomer and a polyfunctional acrylate compound, and wherein the second monomer is a fluorocarbon ester 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 fabric, 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 together with the silane transition layer.

According to at least one embodiment of the present invention, the step of depositing a silane transition layer further comprises the steps of:

introducing auxiliary gas into a reaction cavity of a reaction device; and

then introducing organosilane raw materials 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 step of depositing the coating layer, a first monomer and a second monomer are introduced into a reaction chamber of a reaction device to form the coating layer under a plasma environment, wherein the first monomer is a low dipole moment organic monomer and/or a multifunctional acrylate compound, and the second monomer is a fluorocarbon ester compound.

According to at least one embodiment of the invention, in the above method, the deposition of the silane transition layer and the coating layer respectively comprises a pretreatment stage and a coating stage, wherein in the pretreatment stage, the plasma discharge power is 120-500W and the discharge duration is 60-500 s, and in the coating stage, the plasma discharge power is 10-180W and the discharge duration is 400-7200 s.

According to at least one embodiment of the present invention, in the above method, the plasma discharge manner is an electrodeless discharge, a single electrode discharge, a double electrode discharge, or a multiple electrode discharge.

According to at least one embodiment of the present invention, in the above method, the silane transition layer is prepared using organosilane and a resist solution as raw materials.

According to at least one embodiment of the present invention, in the above method, the organosilane includes 0 to 100 parts by mass of a hydrophilic silane and 50 to 100 parts by mass of a hydrophobic silane.

Detailed Description

The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art. The basic principles of the invention, as 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 is understood that the terms "a" and "an" should be interpreted as meaning that a number of one element or element is one in one embodiment, while a number of other elements is one in another embodiment, and the terms "a" and "an" 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 the 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, namely, the silane transition layer is positioned between the surface of the substrate and the coating layer.

The silane transition layer can be prepared by respectively taking hydrophobic silane and hydrophilic silane as raw materials, or taking hydrophobic silane and hydrophilic silane as raw materials together. In particular, when the silane transition layer is made of hydrophobic silane and hydrophilic silane together as raw materials, the hydrophilic silane may improve the binding force between the metal substrate and the coating layer, and the hydrophobic silane may improve the hydrophobic property of the silane transition layer itself.

Further, the silane raw material of the silane transition layer may 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, and the corrosion resistance of the whole base material is favorably improved.

The invention provides a product of a composite protective film layer with the silane transition layer, and 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 is attached to the surface of electronic products, silk fabrics, woven bags, metal products, glass products and ceramic products, the composite protective film can protect the products, for example, the products have better corrosion resistance.

The invention provides a preparation method of a composite protective film layer with the silane transition layer, wherein the composite protective film layer is formed on the surface of a base material 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, plasma is formed in the reaction chamber, and then the silane transition layer is formed on the substrate surface through the deposition reaction of silane raw material. And then forming the coating on the outer side of the silane transition layer through a reaction raw material deposition reaction for preparing the coating, thereby obtaining the composite protective film layer with the silane transition layer.

Plasma enhanced chemical vapor deposition processes have many advantages over other existing deposition processes: (1) dry film formation does not require the use of organic solvents; (2) the plasma acts on the surface of the substrate in an etching way, so that the deposited film has good adhesion with the substrate; (3) the coating can be uniformly deposited on the surface of the irregular matrix, and the gas phase permeability is extremely strong; (4) the coating has good designability, and compared with the micron-scale control precision of a liquid phase method, the chemical vapor phase method can control the thickness of the coating at a nanoscale scale; (5) the coating structure is easy to design, the chemical vapor method uses plasma for activation, a specific initiator is not required to be designed for initiating the composite coatings of different materials, and various raw materials can be compounded together by regulating and controlling input energy; (6) the compactness is good, the chemical vapor deposition method usually activates a plurality of active sites in the plasma initiation process, and is similar to the situation that a plurality of functional groups are arranged on one molecule in the solution reaction, and a cross-linking structure is formed among molecular chains through the plurality of functional groups; (7) as a coating treatment technical means, the coating treatment method has excellent universality, and the selection range of coating objects and raw materials 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, electric spark discharge and the like.

According to an embodiment of the present invention, the preparation method comprises the steps of:

1) substrate preparation

A cleaning process is required for the substrate before the chemical vapor deposition is performed on the substrate. Dust, moisture or grease on the surface of the substrate can adversely affect the deposition effect. The substrate may be cleaned with acetone or isopropanol and then dried in a drying oven.

2) Chemical vapor deposition of a substrate to produce a silane transition layer

(1) Placing a substrate in the reaction cavity of the reaction device, vacuumizing to 10-200 mTorr, and introducing auxiliary gas, such as He, Ar and O₂Or a mixture of several.

(2) Introducing silane raw materials or monomer steam doped with corrosion inhibitors 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 with the silane transition layer to obtain a composite protective film layer

Introducing first monomer steam and second monomer steam into the reaction cavity on the surface of the substrate with the prepared silane transition layer until the vacuum degree is 30-300 millitorr, starting plasma discharge, performing chemical vapor deposition, and forming 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 restore the reaction cavity of the reaction device to normal pressure. And then taking out the substrate prepared with the composite protective film layer from the reaction cavity.

According to the embodiment of the invention, the steps of preparing and forming the composite film layer on the basis of the silane transition layer preparation step and the silane transition layer respectively comprise two stages, wherein one stage is a pretreatment stage, and the other stage is a coating stage (comprising the steps of preparing the transition layer and preparing a coating), in the pretreatment stage, the plasma discharge power is 120-500W, and the continuous discharge time is 60-500 s. In the coating stage, the plasma discharge power is 10-180W, and the continuous discharge time is 400-7200 s. That is to say, in the pretreatment stage in the silane transition layer preparation step, the plasma discharge power is 120-500W, and the sustained discharge time is 60-500 s, in the coating stage in the silane transition layer preparation step, the plasma discharge power is 10-180W, and the sustained discharge time is 400-7200 s. In the step of preparing and forming the composite film layer on the basis of the silane transition layer, the plasma discharge power is 120-500W in the pretreatment stage, 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 is 10-180W, and the continuous discharge time is 400-7200 s.

Plasma discharges that may be used in accordance with embodiments of the present invention may be electrodeless discharges (e.g., rf inductively coupled discharges, microwave discharges), single electrode discharges (e.g., corona discharges, plasma jets formed from unipolar discharges), double electrode discharges (e.g., dielectric barrier discharges, bare electrode rf glow discharges), and multiple electrode discharges (e.g., discharges using a 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, the reaction chamber may be a rotating body-shaped chamber or a cubic body-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 ℃, and the flow rate of the inert gas is 5 to 300 sccm.

According to an embodiment of the present invention, in the step of preparing the silane transition layer, the feeding mode of the introduced gas may be one of a single feeding mode, an integral two-feeding mode or a three-way feeding mode, for example, when the introduced gas is He, Ar and O₂In this case, the feeding may be performed by a three-way feeding method, such as a Y-type three-way feeding method.

According to an embodiment of the present invention, in the silane transition layer preparation step, the feeding manner of the first monomer and the second monomer may be performed through different feeding channels, for example, two feeding channels are integrated, so that the monomers that react with each other are prevented from reacting in the conventional single-port feeding channel. The silane feedstock and corrosion inhibitor may be fed through different feed channels, such as a tee feed.

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: benzotriazole, benzimidazole, 2-sulfenyl-1-methylimidazole, dimercapto thiadiazole, 1-phenyl-4-methylimidazole, pyrazoline, tetrazole, uracil, 5-amino uracil, 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: one or more of rare earth nitrates such as lanthanum nitrate, cerium nitrate, molybdenum nitrate, erbium nitrate, zirconium nitrate, cobalt nitrate, yttrium nitrate, scandium nitrate, indium nitrate and the like.

Further, the corrosion inhibitor may be dissolved in an organic solvent selected from the group consisting of the combinations: one of benzenes and derivatives thereof such as water, formamide, trifluoroacetic acid, DMSO, acetonitrile, DMF, hexamethylphosphoramide, methanol, ethanol, acetic acid, isopropanol, isoamyl alcohol, divinylbenzene, and p-xylene.

According to an embodiment of the present invention, in the silane transition layer preparation step, the silane raw material may be of the following general formula Y-R-SiX₃The silane compound of (1), wherein when the silane raw material is a hydrophilic silane, the hydrophilic silane Y is one of urea group, carboxylic acid, ether group, amino group, etc., and wherein when the silane raw material is a hydrophobic silane, the hydrophobic silane Y is a hydrocarbon group, a sulfur group, an ester group, a phenyl group, an epoxy group. R is one of organic carbon chains including C-C, C ═ C, C-N-C, C-S-C and the like. X is one or more of methoxyl, ethoxyl, chlorine, bromine, acetoxyl, amino, etc.

According to embodiments of the present invention, when the silane starting material is a hydrophilic silane, the silane starting material may be selected from the group consisting of: one or more of ureidopropyltriethoxysilane, ureidopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, 2-aminoethyl-aminopropyltrimethoxysilane, diethylenetriaminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane and diethylenetriaminopropyltrimethoxysilane.

According to embodiments of the present invention, when the silane starting material is a hydrophobic silane, the silane starting material may be selected from the group consisting of: phenyltriethoxysilane, vinylpropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethylsilane, 3-butenyltrimethylsilane, vinyltributketoximosilane, tetramethyldivinyldisiloxane, 1,2, 2-trifluorovinyltriphenylsilane, hexaethylcyclotrisiloxane, 3- (methacryloyloxy) propyltrimethoxysilane, phenyltris (trimethylsiloxy) silane, diphenyldiethoxysilane, triphenylchlorosilane, methylvinyldichlorosilane, trifluoropropyltrichlorosilane, trifluoropropylmethyldichlorosilane, dimethylphenylchlorosilane, tributylchlorosilane, benzyldimethylchlorosilane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, hexaphenylcyclotrisiloxane, decamethylcyclopentasiloxane, octaphenylcyclotetrasiloxane, vinyltrimethylsiloxane, One or more of triphenylhydroxysilane, diphenyldihydroxysilane, trifluoropropylmethylcyclotrisiloxane, 2,4, 4-tetramethyl-6, 6,8, 8-tetraphenylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, 3-glycidoxypropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, decamethylcyclopentasiloxane, thiopropyltrimethoxysilane and bis- [ gamma- (triethoxysilyl) propyl ] -tetrasulfide.

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 organic corrosion inhibitor and/or the inorganic corrosion inhibitor accounts for 0-80 parts by mass of the corrosion inhibitor solution. The silane raw material can be composed of the following components in parts by mass: 0-100 parts of hydrophilic silane and 50-100 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 1000 ul/min.

According to an embodiment of the present invention, in the step of preparing and forming the composite film layer on the basis of the silane transition layer, the first monomer may be one or more of a low dipole moment organic monomer or a multifunctional acrylate.

When the first monomer is a low dipole moment organic monomer, it may be selected from the group consisting of: p-xylene, benzene, toluene, carbon tetrafluoride, alpha-methylstyrene, poly-p-dichlorotoluene, dimethylsiloxane, 500-molecular-weight 50000-polydimethylsiloxane, allylbenzene, decafluorobiphenyl, perfluoroallylbenzene, tetrafluoroethylene, hexafluoropropylene, 1H-perfluorooctylamine, perfluoroiodododecane, perfluorotributylamine, 1, 8-diiodoperfluorooctane, perfluorohexyliodoalkane, perfluoroiodobutane, perfluoroiododecane, perfluorooctyliodoalkane, 1, 4-bis (2 ',3' -epoxypropyl) perfluorobutane, dodecafluoro-2-methyl-2-pentene, 2- (perfluorobutyl) ethyl methacrylate, 2- (perfluorooctyl) iodoethane, dimethyl-p-dimethylsiloxane, 1H-perfluorooctyl-amine, perfluoroiodododecane, perfluorotributyl-n-e, perfluoroiodobutane, perfluorooctyl-n-e, perfluorooctyl) ethyl methacrylate, 2- (perfluorooctyl) iodoethane, dimethyl-co-butyl), One or more of perfluorodecyl ethyl iodide, 1,2, 2-tetrahydroperfluorohexyl iodide, perfluorobutyl ethylene, 1H, 2H-perfluoro-1-decene, 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 1,1,4, 4-tetraphenyl-1, 3-butadiene.

When the first monomer is a polyfunctional acrylate compound, it may be 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, tert-butyl methacrylate, glycidyl methacrylate, trimethylsilyl methacrylate and diethylene glycol dimethacrylate.

According to an embodiment of the present invention, in the step of preparing and forming the composite film layer on the basis of the silane transition layer, the second monomer may be a monofunctional fluorocarbon ester compound, and may be selected from a combination of: 3- (perfluoro-5-methyl hexyl) -2-hydroxypropyl methacrylate, 2- (perfluoro decyl) ethyl methacrylate, 2- (perfluoro hexyl) ethyl methacrylate, 2- (perfluoro dodecyl) ethyl acrylate, 2-perfluoro octyl ethyl acrylate, 1H,2H, 2H-perfluoro octanol acrylate, 2- (perfluoro butyl) ethyl acrylate, (2H-perfluoro propyl) -2-acrylate, (perfluoro cyclohexyl) methacrylate, 3,3, 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 be in a range of 10 to 1000 ul/min.