Composite coatings, manufacturing methods and devices

Abstract

A specific embodiment of the present invention provides a composite coating, manufacturing method, and device, comprising Coating I and Coating II, where Coating I is formed by plasma polymerization of a silane monomer containing an active functional group having affinity or reactivity with polymer molecules and a hydrolyzable group such as a halogen atom, an alkoxy group, or an acyloxy group, and Coating II is formed by vacuum vapor deposition of parylene on Coating I, and the composite coating improves the bonding strength and coverage of the parylene coating to the substrate.

Description

[Technical Field]

[0001] This application claims priority from a Chinese patent application filed with the China Patent Office on December 22, 2022, with application number 202211657165.7 and titled "Composite Coating, Manufacturing Method and Device," the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to the field of vacuum vapor deposition, and in particular to composite coatings, manufacturing methods and devices. [Background technology]

[0003] Parylene, a protective polymer material known as poly-paraxylene in Chinese, is classified into various types, including N-type, C-type, D-type, F-type, and HT-type, based on its molecular structure. It is a new type of conformal coating material developed and applied by the U.S.-based Union Carbide Co. in the mid-1960s. Parylene can be vapor-deposited under vacuum. The excellent penetration of Parylene's active molecules allows it to form pinhole-free, uniformly thick, transparent insulating coatings on the interior, exterior, and periphery of electronic components, providing a complete, high-quality protective coating that resists damage from acids, alkalis, salt spray, mildew, and various corrosive gases. However, due to the characteristics of its molecular structure, the coating's surface energy range is relatively uniform. Furthermore, its manufacturing method involves high-temperature decomposition followed by low-temperature deposition on the substrate surface, resulting in weak bonding with the substrate, primarily relying on intermolecular van der Waals forces rather than chemical bonding. These factors significantly limit its application scenarios. Summary of the Invention

[0004] As described above, currently, parylene coatings have a single application range and weak bonding strength between the coating and the substrate. In response to the above-mentioned problems, specific embodiments of the present invention provide a composite coating, manufacturing method, and device that can be combined with a PECVD coating to improve bonding strength and application range with the substrate. The specific scheme is as follows:

[0005] A composite coating comprising Coating I and Coating II, The coating I is a plasma-polymerized coating formed by contacting a substrate with a plasma containing a monomer α, the monomer α having the structure shown in formula (1): JPEG2025539603000001.jpg1517(1) In formula (1), R1 is a vinyl group or a C1-C 10 wherein the substituent of the substituted alkyl group contains at least one of a halogen atom, an alkenyl group, an alkynyl group, a hydrocarbyloxy group, an amino group, an epoxy group, an acyloxy group, an amido group, a hydroxy group, and a mercapto group, and R2, R3, and R4 each independently represent a halogen atom, a C1-C 10 Alkoxy groups, C1-C 10 Substituted alkoxy groups of C1-C 10 or an acyloxy group of C1 to C 10 substituted acyloxy groups selected from the group consisting of: Coating II is a parylene coating formed on Coating I by vacuum vapor deposition, forming a composite coating.

[0006] Optionally, R1 is a vinyl group, a glycidyloxypropyl group, an acryloyloxypropyl group, a methacryloyloxypropyl group, an N-(β-aminoethyl)-γ-aminopropyl group, an N-(β-aminoethyl)-γ-aminopropyl-methyl group, a chloropropyl group, a mercaptopropyl group, a hydroxypropyl group, or an aminopropyl group, and R2, R3, and R4 are a chlorine atom, a methoxy group, an ethoxy group, or a methoxyethoxy group.

[0007] Optionally, the monomer a is selected from the group consisting of vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane, γ-glycidyloxypropyl-trimethoxysilane, γ-glycidyloxypropyl-triethoxysilane, 3-(acryloyloxy)propyltrimethoxysilane, γ-methacryloyloxypropyl-trimethoxysilane, γ-methacryloyloxypropyl-triethoxysilane, N-(β-aminoethyl)-γ-aminopropyl-methyl-trimethoxysilane, The silane may be selected from at least one of N-(β-aminoethyl)-γ-aminopropyl-methyl-triethoxysilane, N-(β-aminoethyl)-γ-aminopropyl-trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl-triethoxysilane, γ-chloropropyl-trimethoxysilane, γ-chloropropyl-triethoxysilane, γ-mercaptopropyl-trimethoxysilane, γ-mercaptopropyl-triethoxysilane, γ-aminopropyl-trimethoxysilane, or γ-aminopropyl-triethoxysilane.

[0008] Optionally, said monomer a is γ-aminopropyltriethoxysilane.

[0009] Optionally, the composite coating further comprises a coating III that is a plasma-polymerized hydrophobic coating or a plasma-polymerized hydrophilic coating formed by contacting the coating II with a plasma comprising monomer β.

[0010] Optionally, the monomer β has the structure shown in formula (2): JPEG2025539603000002.jpg424(2) In formula (2), R5 is a bond, a C1-C4 alkylene group or a C1-C4 halogenated alkylene group, Y is a halogen atom, a hydrogen atom, a hydroxy group or a structure represented by the following formula (3) or (4), and n is an integer of 1 to 12. JPEG2025539603000003.jpg23161(3) (4) In formula (3), R6, R7, and R8 are each independently selected from a hydrogen atom, a halogen atom, a C1-C4 alkyl group, or a C1-C4 halogenated alkyl group, and X is a bond or an ester bond; In formula (4), R9, R 10 and R 11 are each independently selected from a hydrogen atom, a C1 to C4 alkyl group, a C1 to C4 halogenated alkyl group, a C1 to C4 alkoxy group, or a C1 to C4 halogenated alkoxy group.

[0011] Optionally, the monomer β has a structure shown in formula (5): JPEG2025539603000004.jpg2043(5) In formula (5), m is an integer of 0 to 4.

[0012] Optionally, R6, R7 and R8 are each independently selected from a hydrogen atom or a methyl group; m is an integer of 0-2; and n is an integer of 1-10.

[0013] Optionally, said monomer β is 2-perfluorohexylethyl acrylate.

[0014] Optionally, the monomer β has the structure shown in formula (6): JPEG2025539603000005.jpg2035(6) In formula (6), R 12 , R 13 and R 14 are each independently selected from a hydrogen atom, a halogen atom, a C1-C4 alkyl group, or a C1-C4 halogenated alkyl group; R 15 is a bond, a C1-C4 alkylene group, or a C1-C4 halogenated alkylene group, and R 16 , R 17 and R 18are each independently selected from a hydrogen atom, a C1 to C4 alkyl group, a C1 to C4 halogenated alkyl group, a C1 to C4 alkoxy group, or a C1 to C4 halogenated alkoxy group, and Y is a bond or an oxygen atom.

[0015] Optionally, the monomer β has the structure shown in formula (7): JPEG2025539603000006.jpg1524(7) In formula (7), R 19 is a C1-C4 amide group, a C1-C4 substituted alkoxy group, a C1-C4 substituted alkyl group, or a C1-C4 substituted ester group, and R 20 , R 21 and R 22 are each independently selected from a hydrogen atom, a C1 to C4 amide group, a C1 to C4 substituted alkoxy group, a C1 to C4 substituted alkyl group, a C1 to C4 substituted ester group, or a C1 to C4 hydrocarbyl group; The substituents of the C1 to C4 substituted alkoxy group, C1 to C4 substituted alkyl group and C1 to C4 substituted ester group are a hydroxy group, a carboxy group or an amino group.

[0016] Optionally, said R 19 is a C1-C4 hydroxyalkyl ester group, and R 20 , R 21 and R 22 are each independently selected from a hydrogen atom or a methyl group.

[0017] Optionally, the monomer β is selected from at least one of acrylic acid, methacrylic acid, 3,3-dimethylacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, 1-buten-3-ol, 2-butene-1,4-diol, 3-penten-2-ol, cis-3-hexen-1-ol, methallyl alcohol, 2,7-octadien-1-ol, Nt-butylacrylamide, glycerol dimethacrylate, N,N-diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, or N,N-dimethylacrylamide.

[0018] Optionally, the coating III is a plasma-polymerized hydrophobic coating or a plasma-polymerized hydrophilic coating formed by contacting the coating II with a plasma containing a monomer β and a monomer δ, wherein the monomer δ has the structure shown in formula (8): JPEG2025539603000007.jpg2053(8) In formula (8), R 24 , R 25 , R 26 , R 27 , R 28 and R 29 are each independently a hydrogen atom, C1 to C 10 or C1-C 10 R is selected from halogen atom-substituted alkyl groups 23 is the linking site.

[0019] Optionally, the monomer δ has the structure shown in formula (9): JPEG2025539603000008.jpg2057(9) In formula (9), R 30 is C2~C 10 or an alkylene group of C2 to C 10 and a is an integer of 1 to 10.

[0020] Optionally, said R 24 , R 25 , R 26 , R 27 , R 28 and R 29 are each independently selected from a hydrogen atom or a methyl group, and a is an integer of 1 to 4.

[0021] Optionally, the monomer δ is selected from at least one of 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, or neopentyl glycol dimethacrylate.

[0022] A method for producing a composite coating as described above, comprising the steps of: providing a substrate, placing the substrate in a vacuum growth chamber, introducing a gaseous monomer α into the vacuum growth chamber, generating a plasma discharge, and plasma polymerizing the monomer α on the substrate surface to form the coating I; and and introducing parylene powder into the vacuum growth chamber after sublimation and decomposition, to form coating II on coating I.

[0023] Optionally, the method further comprises introducing gaseous monomer β, or gaseous monomer β and monomer δ, into the vacuum growth chamber, plasma discharging, and plasma polymerizing on the surface of coating II to form coating III.

[0024] A device, at least a portion of whose surface has a composite coating as described above.

[0025] In a specific embodiment of the composite coating of the present invention, the composite coating includes Coating I and Coating II. Coating I is formed by plasma polymerization of a silane monomer containing an active functional group that has affinity or reactivity with polymer molecules and a hydrolyzable group such as a halogen atom, an alkoxy group, or an acyloxy group. Coating II is formed by vacuum vapor deposition of parylene on Coating I. The composite coating improves the bonding strength and coverage of the parylene coating to the substrate. DETAILED DESCRIPTION OF THE INVENTION

[0026] A specific embodiment of the present invention provides a composite coating, the composite coating comprising Coating I and Coating II, The coating I is a plasma-polymerized coating formed by contacting a substrate with a plasma containing a monomer α, the monomer α having the structure shown in formula (1): JPEG2025539603000009.jpg1517(1) In formula (1), R1 is a vinyl group or a C1-C 10 wherein the substituent of the substituted alkyl group contains at least one of a halogen atom, an alkenyl group, an alkynyl group, a hydrocarbyloxy group, an amino group, an epoxy group, an acyloxy group, an amido group, a hydroxy group, and a mercapto group, and R2, R3, and R4 each independently represent a halogen atom, a C1-C 10 Alkoxy groups, C1-C 10 Substituted alkoxy groups of C1-C 10 or an acyloxy group of C1 to C 10 substituted acyloxy groups selected from the group consisting of: Coating II is a parylene coating formed on Coating I by vacuum vapor deposition.

[0027] In a specific embodiment of the composite coating of the present invention, R1 is C1 to C 10 The term "substituted alkyl group" means that R1 is a C1-C 10wherein the substituent is an active group such as a halogen atom, an alkenyl group, an alkynyl group, a hydrocarbyloxy group, an amino group, an epoxy group, an acyloxy group, an amido group, a hydroxy group, or a mercapto group, and the active group has affinity or reactivity with a polymer molecule. In some specific embodiments, R is a vinyl group, a glycidyloxypropyl group, an acryloyloxypropyl group, a methacryloyloxypropyl group, an N-(β-aminoethyl)-γ-aminopropyl group, an N-(β-aminoethyl)-γ-aminopropyl-methyl group, a chloropropyl group, a mercaptopropyl group, a hydroxypropyl group, or an aminopropyl group.

[0028] In the composite coating of a specific embodiment of the present invention, R2, R3, and R4 are each independently selected from the group consisting of a halogen atom, a C1-C 10 Alkoxy groups, C1-C 10 Substituted alkoxy groups of C1-C 10 or an acyloxy group of C1 to C 10 The substituted alkoxy group and substituted acyloxy group refer to alkoxy groups having a substituent and acyloxy groups having a substituent, and the substituent may be a halogen atom or various organic groups such as a hydrocarbyl group, a hydrocarbyloxy group, an ester group, or a ketone group. In some specific embodiments, R2, R3, and R4 are each independently selected from a halogen atom, a C1-C4 alkoxy group, or a C1-C4 acyloxy group, and in some specific embodiments, R2, R3, and R4 are a chlorine atom, a methoxy group, an ethoxy group, or a methoxyethoxy group.

[0029] In the composite coatings of specific embodiments of the present invention, in some specific embodiments, the monomer α is selected from the group consisting of vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane, γ-glycidyloxypropyl-trimethoxysilane, γ-glycidyloxypropyl-triethoxysilane, 3-(acryloyloxy)propyltrimethoxysilane, γ-methacryloyloxypropyl-trimethoxysilane, γ-methacryloyloxypropyl-triethoxysilane, N-(β-aminoethyl)-γ-aminopropyl-methyl-trimethoxysilane, N-( and at least one of N-(β-aminoethyl)-γ-aminopropyl-methyl-triethoxysilane, N-(β-aminoethyl)-γ-aminopropyl-trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl-triethoxysilane, γ-chloropropyl-trimethoxysilane, γ-chloropropyl-triethoxysilane, γ-mercaptopropyl-trimethoxysilane, γ-mercaptopropyl-triethoxysilane, γ-aminopropyl-trimethoxysilane, or γ-aminopropyl-triethoxysilane, and in some specific embodiments, the monomer α is γ-aminopropyltriethoxysilane.

[0030] In a specific embodiment of the composite coating of the present invention, the parylene coating comprises a coating formed by vacuum vapor deposition of N-type parylene, C-type parylene, D-type parylene, F-type parylene, or HT-type parylene.

[0031] In some specific embodiments of the composite coating of the present invention, the composite coating further comprises a coating III, which is a plasma-polymerized hydrophobic coating formed by contacting the coating II with a plasma containing a monomer β, and the monomer β has a structure containing a perfluoro segment as shown in the following formula (2): JPEG2025539603000010.jpg424(2) In formula (2), R5 is a bond, a C1-C4 alkylene group or a C1-C4 halogenated alkylene group, Y is a halogen atom, a hydrogen atom, a hydroxy group or a structure represented by the following formula (3) or (4), and n is an integer of 1 to 12. Specifically, n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.

[0032] JPEG2025539603000011.jpg21161(3) (4) In formula (3), R6, R7, and R8 are each independently selected from a hydrogen atom, a halogen atom, a C1-C4 alkyl group, or a C1-C4 halogenated alkyl group; X is a bond or an ester bond; in some specific embodiments, R6, R7, and R8 are each independently selected from a hydrogen atom or a methyl group; in some specific embodiments, R6 and R8 are hydrogen atoms, and R7 is a hydrogen atom or a methyl group; in formula (4), R9, R 10 and R 11 are each independently selected from a hydrogen atom, a C1-C4 alkyl group, a C1-C4 halogenated alkyl group, a C1-C4 alkoxy group, or a C1-C4 halogenated alkoxy group. Specific examples of the C1-C4 alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, or an isobutylene group. Specific examples of the C1-C4 alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, or an isobutyl group. Specific examples of the C1-C4 alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, or an isobutoxy group. The term "halogenated" means that at least one hydrogen atom on the carbon chain is substituted with a halogen atom. In some specific embodiments, the monomer β has a structure represented by the following formula (5): JPEG2025539603000012.jpg2043(5) In formula (5), m is an integer of 0 to 4, specifically 0, 1, 2, 3, or 4. In some specific embodiments, in consideration of environmental impact, n is an integer of 1 to 10, and further n is an integer of 1 to 7. In some specific embodiments, the monomer β is selected from one or more of 2-(perfluorodecyl)ethyl methacrylate, 2-(perfluorohexyl)ethyl methacrylate, 2-(perfluorododecyl)ethyl acrylate, 2-(perfluorooctyl)ethyl acrylate, 1H,1H,2H,2H-perfluorooctyl acrylate, and 2-(perfluorobutyl)ethyl acrylate, and in some specific embodiments, the monomer β is 2-perfluorohexylethyl acrylate.

[0033] In the composite coating of the specific embodiment of the present invention, in some specific embodiments, the monomer β has a structure shown in formula (6) below: JPEG2025539603000013.jpg2035(6) In formula (6), R 12 , R 13 and R 14 are each independently selected from a hydrogen atom, a halogen atom, a C1-C4 alkyl group, or a C1-C4 halogenated alkyl group; R 15 is a bond, a C1-C4 alkylene group, or a C1-C4 halogenated alkylene group, and R 16 , R 17 and R 18are each independently selected from a hydrogen atom, a C1-C4 alkyl group, a C1-C4 halogenated alkyl group, a C1-C4 alkoxy group, or a C1-C4 halogenated alkoxy group, and Y is a bond or an oxygen atom. Specific examples of the C1-C4 alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, and an isobutylene group. Specific examples of the C1-C4 alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group. Specific examples of the C1-C4 alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and an isobutoxy group. The term "halogenated" means that at least one hydrogen atom on the carbon chain is substituted with a halogen atom.

[0034] In the composite coating of specific embodiments of the present invention, in some specific embodiments, the coating III is a plasma-polymerized hydrophilic coating formed by contacting the coating II with a plasma containing a monomer β, and in some specific embodiments, the monomer β has a structure shown in formula (7) below. JPEG2025539603000014.jpg1524(7) In formula (7), R 19 is a C1-C4 amide group, a C1-C4 substituted alkoxy group, a C1-C4 substituted alkyl group, or a C1-C4 substituted ester group, and R 20 , R 21 and R 22are each independently selected from a hydrogen atom, a C1-C4 amide group, a C1-C4 substituted alkoxy group, a C1-C4 substituted alkyl group, a C1-C4 substituted ester group, and a C1-C4 hydrocarbyl group, and the substituents of the C1-C4 substituted alkoxy group, C1-C4 substituted alkyl group, and C1-C4 substituted ester group are hydrophilic groups such as a hydroxy group, a carboxy group, or an amino group. The C1-C4 substituted alkoxy group, C1-C4 substituted alkyl group, or C1-C4 substituted ester group refers to a C1-C4 alkoxy group, C1-C4 alkyl group, or C1-C4 ester group having the hydroxy group, carboxy group, or amino group as a substituent. In some specific embodiments, the monomer β is acrylic acid, methacrylic acid, 3,3-dimethylacrylic acid, 2-butene-1,4-diol, 3-penten-2-ol, cis-3-hexen-1-ol, methallyl alcohol, 2,7-octadien-1-ol, Nt-butylacrylamide, glycerol dimethacrylate, N,N-diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, or N,N-dimethylacrylamide. 19 is a C1 to C4 hydroxyalkyl ester group such as a hydroxymethyl ester group, a hydroxyethyl ester group, a hydroxypropyl ester group, or a hydroxybutyl ester group, and 20 , R 21 and R 22 are each independently selected from a hydrogen atom or a methyl group, and in some specific embodiments, 20 is a hydrogen atom or a methyl group, 21 and R 22 is a hydrogen atom, and in some specific embodiments, said monomer β is hydroxyethyl acrylate, hydroxypropyl acrylate, or hydroxyethyl methacrylate.

[0035] In some specific embodiments of the composite coating of the present invention, the coating III is a plasma-polymerized hydrophobic coating or a plasma-polymerized hydrophilic coating formed by contacting the coating II with a plasma containing a monomer β and a monomer δ, wherein the monomer δ has the structure shown in formula (8): JPEG2025539603000015.jpg2053(8) In formula (8), R 24 , R 25 , R 26 , R 27 , R 28 and R 29 are each independently a hydrogen atom, C1 to C 10 or C1-C alkyl group 10 R is selected from halogen atom-substituted alkyl groups 23 is a linking moiety. In some specific embodiments, R 24 , R 25 , R 26 , R 27 , R 28 and R 29 are each independently selected from a hydrogen atom, a C1-C4 alkyl group, or a C1-C4 halogen atom-substituted alkyl group, and in some specific embodiments, R 24 , R 25 , R 26 , R 27 , R 28 and R 29 are each independently selected from a hydrogen atom or a methyl group, and in some specific embodiments, 25 and R 28 is a hydrogen atom or a methyl group, R 24 , R 26 , R 27 and R 29 is a hydrogen atom. 23is a linking moiety and may be, for example, an alkylene group, an alkylene group having a substituent, or an alkylene group having an O or S atom or a carbonyl group between the carbon-carbon bond, and the substituent may be any of various organic groups, specifically, for example, a halogen atom, a hydroxy group, a hydroxyhydrocarbyl group, an arylhydrocarbyl group, an ester group, a hydrocarbyloxy group, a ketone group, etc. In some specific embodiments, the monomer δ has a structure represented by the following formula (9): JPEG2025539603000016.jpg2057(9) In formula (9), R 30 is C2~C 10 or an alkylene group of C2 to C 10 wherein a is an integer of 1 to 10, specifically 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, and an isobutylene group, and in some specific embodiments, a is an integer of 1 to 4. In some specific embodiments, the monomer δ is selected from at least one of 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, and neopentyl glycol dimethacrylate.

[0036] In the composite coatings of specific embodiments of the present invention, in some specific embodiments, Coating I is a plasma polymerized coating formed by plasma of monomer α, and in other specific embodiments, Coating I may be a plasma polymerized coating formed by plasma of monomer α plus other appropriate monomers without affecting the overall coating performance of Coating I. In some specific embodiments, Coating III is a plasma polymerized coating formed by contacting Coating II with plasma of monomer β, and in some specific embodiments, Coating III is a plasma polymerized coating formed by contacting Coating II with plasma of monomer β and monomer δ, and in other specific embodiments, Coating III is formed by plasma of other appropriate monomers without affecting the overall coating performance of Coating III.

[0037] In the composite coating of the present invention, in some specific embodiments, the molar ratio of the monomer β to the monomer δ is between 3:10 and 10:3, and may be, for example, 3:10, 4:10, 5:10, 6:10, 7:10, 8:10, 9:10, 10:10, 10:9, 10:8, 10:7, 10:6, 10:5, 10:4, or 10:3. In other specific embodiments, as long as both protective performance and transparency are satisfied, other ratios may be adjusted according to the specific monomer conditions.

[0038] In the composite coating of specific embodiments of the present invention, in some specific embodiments, the substrate is various plastics, metals, fabrics, glass, electrical components, optical devices, etc. Specifically, the electrical components may be printed circuit boards (PCBs), electronic products, or electronic semi-assembled products, etc. When the substrate is an electronic product, examples include, but are not limited to, mobile phones, tablets, keyboards, e-readers, wearable devices, displays, etc. The substrate may be any suitable electrical component of an electrical component, specifically, the electrical component may be a sensor, resistor, capacitor, transistor, diode, amplifier, relay, transformer, battery, fuse, integrated circuit, switch, LED, LED display, piezoelectric element, optoelectronic component, antenna, oscillator, etc.

[0039] In the composite coating of specific embodiments of the present invention, in some specific embodiments, the substrate is a substrate that has been surface treated, for example, by plasma surface treatment, thermal oxygen surface treatment, application of another coating, etc.

[0040] A specific embodiment of the present invention further provides a method for manufacturing the above-mentioned composite coating, the method including: providing a substrate; placing the substrate in a vacuum growth chamber; introducing gaseous monomer α into the vacuum growth chamber, generating a plasma discharge, and plasma polymerizing the monomer α on the substrate surface to form Coating I; and introducing parylene powder into the vacuum growth chamber after sublimation and decomposition to form Coating II on Coating I.

[0041] In some specific embodiments of the method for producing the coating of the present invention, the method further includes placing the substrate having Coating I and Coating II in a vacuum growth chamber, introducing gaseous monomer β, or gaseous monomer β and monomer δ, into the vacuum growth chamber, generating a plasma discharge, and plasma polymerizing the monomer β on the surface of Coating II to form Coating III.

[0042] In the coating manufacturing method of this specific embodiment of the present invention, the parylene vacuum deposition process can be a typical parylene vacuum deposition process, in which parylene powder material is placed in an evaporation furnace of a coating device, the solid raw material is sublimated into gas under vacuum conditions and at a high temperature of 80°C to 200°C, and the gaseous raw material is further decomposed into reactive monomers under high-temperature pyrolysis conditions of 600°C to 750°C, and the gaseous monomers are deposited and polymerized at room temperature to form the parylene coating II.

[0043] In the method for producing the composite coating of the specific embodiment of the present invention, the monomer α, the monomer β, the monomer δ, the parylene material, the substrate, etc. are the same as those described above.

[0044] In the method for producing the composite coating according to the specific embodiment of the present invention, in order to further enhance the bonding strength between the plasma coating and the substrate, in some specific embodiments, the substrate is pretreated with plasma before coating. Specific pretreatment methods include, for example, continuous discharge pretreatment under an inert gas atmosphere with a discharge power of 100 to 600 W and a discharge time of 60 to 3600 s, or pulse discharge pretreatment with a pulse duty ratio of 0.1 to 70%, a pulse frequency of 10 to 500 Hz, a discharge power of 10 to 500 W, and a discharge time of 60 to 3600 s. In other specific embodiments, the substrate is pretreated with heat, oxygen, high-energy radiation, or the like before coating.

[0045] In some specific embodiments of the coating manufacturing method of the present invention, the flow rate of the monomer α, monomer β, monomer δ, or the mixed monomer of monomer β and monomer δ is 10 to 2400 μL / min, specifically, for example, 10 μL / min, 50 μL / min, 100 μL / min, 200 μL / min, 300 μL / min, 500 μL / min, 1000 μL / min, 1500 μL / min, 2000 μL / min, or 2400 μL / min. The temperature in the chamber is controlled to 20°C to 80°C, specifically, for example, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, or 80°C. The vaporization temperature of the monomer is 50°C to 120°C, specifically, for example, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, or 120°C. Vaporization occurs under vacuum conditions.

[0046] In some specific embodiments of the method for producing the composite coating of the specific embodiments of the present invention, the plasma is a continuous plasma, and the continuous plasma is generated by applying a continuous voltage discharge, and the discharge power is 10 to 300 W, specifically, for example, 10 W, 50 W, 100 W, 150 W, 200 W, 250 W, or 300 W, and the discharge time is 60 to 36,000 s, specifically, for example, 60 s, 100 s, 200 s, 300 s, 400 s, 500 s, 600 s, 1,000 s, 2,000 s, 3,600 s, 5,000 s, 10,000 s, 20,000 s, or 36,000 s. In some specific embodiments, the plasma is a pulsed plasma, and the pulsed plasma is generated by applying a pulse voltage discharge, and the pulse power is 10 W to 500 W, specifically, for example, 10 W, 50 W, 100 W, 150 W, 200 W, 250 W, 300 W, 350 W, 400 W, 450 W, or 500 W, and the pulse frequency is 10 Hz to 500 Hz, specifically, for example, 10 Hz, 15 Hz, 20 Hz, 25 Hz, 30 Hz, 35 Hz, 40 Hz, 45 Hz, 50 Hz, 100 Hz, 200 Hz, 300 Hz, 400 Hz, or 500 Hz, the pulse duty ratio is 0.1% to 90%, and specifically, for example, 0.1%, 0.5%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or 90%, and the plasma discharge time is 200 s to 36,000 s, and specifically, for example, 200 s, 500 s, 1,000 s, 2,000 s, 3,600 s, 5,000 s, 10,000 s, 20,000 s, or 36,000 s.

[0047] In the method for producing the composite coating of the specific embodiments of the present invention, in some specific embodiments, the plasma discharge method may be any of various existing discharge methods, specifically, for example, electrodeless discharge (e.g., radio frequency inductively coupled discharge, microwave discharge, etc.), single electrode discharge (e.g., corona discharge, plasma jet formed by unipolar discharge, etc.), dual electrode discharge (e.g., dielectric barrier discharge, exposed electrode radio frequency glow discharge, etc.), and multi-electrode discharge (e.g., discharge using a floating electrode as a third electrode, etc.).

[0048] Specific embodiments of the present invention further provide a device, at least a portion of a surface of the device having a composite coating as described above, and in some specific embodiments, some or all of the surface of the device is deposited with the composite coating described above.

[0049] The present disclosure will now be further described with reference to specific examples. [Example]

[0050] Test method description Coating thickness test: Measured using Filmetrics F20-UV-thin film thickness meter from the United States.

[0051] Hydrophobicity angle test: Tested according to GB / T 30447-2013 standard.

[0052] 20.5V Acidic Sweat Immersion: The test procedure was as follows: 1. The power supply supplied 20.5V to the circuit board. 2. The circuit board was immersed in acidic artificial sweat with a pH of 4.7±0.1. 3. The current was detected by a computer. 4. The time to failure (current > 0.6mA) was recorded.

[0053] Black ink gloss plate bonding strength: Detected by measuring the adhesive strength according to the ASTM D3359-2017 standard test method tape method. Example 1

[0054] Parylene C powder and 3-aminopropyltriethoxysilane monomer were charged into their respective supply areas, and silicon wafer, printed circuit board, and black ink gloss plate samples were placed on a rotating holder in a vacuum growth chamber. The rotating holder was turned on and rotated, and the chamber was evacuated to 10 mTorr. Helium gas was introduced at a flow rate of 40 sccm and controlled to stabilize the pressure at 80 mTorr. The chamber temperature was 30°C.

[0055] A continuous plasma discharge was initiated. In this pretreatment stage, the discharge power was 180 W and the discharge continued for 300 seconds. After the surface pretreatment of the silicon wafer, printed circuit board, and black ink gloss plate samples was completed, the discharge was terminated.

[0056] Next, 3-aminopropyltriethoxysilane monomer was introduced into the vaporization chamber, vaporized at a vaporization temperature of 90 °C, and then introduced into the chamber. Pulse plasma discharge was initiated, and plasma chemical vapor deposition was performed. The pulse duty ratio was 8%, the pulse frequency was 50 Hz, the pulse discharge power was 200 W, the flow rate of the monomer introduced into the vaporization chamber was 480 μL / min, and the reaction time was 600 s.

[0057] The discharge was terminated, the monomer supply and helium gas were stopped, and the chamber pressure was controlled to 20 mTorr. The Parylene C powder was heated to 170°C in the sublimation chamber to be sublimated, then introduced into the decomposition chamber and decomposed at a temperature of 690°C. It was then introduced into the chamber and deposited for 4 hours. The undeposited raw material was adsorbed in a cold trap to prevent it from entering the vacuum pump.

[0058] After the coating was completed, compressed air was introduced into the chamber to return it to normal pressure. The coated silicon wafers, printed circuit boards, and black ink glossy plate samples were then removed. The silicon wafers were placed on a rotating holder in three layers, designated A, B, and C, from top to bottom, and the coating thickness and water contact angle were tested. The results are shown in Table 1. The printed circuit boards were placed on a rotating holder in three layers, designated A, B, and C, from top to bottom, and tested for 20.5V acid sweat immersion. The results are shown in Table 1. The black ink glossy plate samples were placed on a rotating holder in three layers, designated A, B, and C, from top to bottom, and the black ink glossy plate bonding strength was tested. The results are shown in Table 1. Example 2

[0059] Parylene C powder and 3-aminopropyltriethoxysilane monomer were charged into their respective supply areas, and silicon wafer, printed circuit board, and black ink gloss plate samples were placed on a rotating holder in a vacuum growth chamber. The rotating holder was turned on and rotated, and the chamber was evacuated to 10 mTorr. Helium gas was introduced at a flow rate of 40 sccm and controlled to stabilize the pressure at 80 mTorr. The chamber temperature was 30°C.

[0060] A continuous plasma discharge was initiated. In this pretreatment stage, the discharge power was set to 180 W and the discharge continued for 300 seconds. After the surface pretreatment of the silicon wafer, printed circuit board, and black ink gloss plate samples was completed, the discharge was terminated.

[0061] Next, 3-aminopropyltriethoxysilane monomer was introduced into the vaporization chamber, vaporized at a vaporization temperature of 90 °C, and then introduced into the chamber. Pulse plasma discharge was initiated, and plasma chemical vapor deposition was performed. The pulse duty ratio was 8%, the pulse frequency was 50 Hz, the pulse discharge power was 200 W, the flow rate of the monomer introduced into the vaporization chamber was 480 μL / min, and the reaction time was 600 s.

[0062] The discharge was terminated, the monomer supply and helium gas were stopped, and the chamber pressure was controlled to 20 mTorr. The Parylene C powder was heated to 170°C in the sublimation chamber to be sublimated, then introduced into the decomposition chamber and decomposed at a temperature of 690°C. It was then introduced into the chamber and deposited for 4 hours. The undeposited raw material was adsorbed in a cold trap to prevent it from entering the vacuum pump.

[0063] Next, the valves connecting the parylene decomposition furnace and the chamber were closed, and He gas was again introduced at a flow rate of 20 sccm. The pressure was controlled at 80 mTorr and stabilized. After stabilization, a 4:1 mass ratio mixture of 2-perfluorohexylethyl acrylate and 1,6-hexanediol diacrylate was introduced into the vaporization chamber. The mixture was vaporized at a vaporization temperature of 90°C and introduced into the chamber. A pulsed plasma discharge was initiated, and plasma-enhanced chemical vapor deposition was performed. The pulse duty ratio was 10%, the frequency was 50 Hz, the discharge power was 150 W, the monomer flow rate was 150 μL / min, and the reaction time was 1800 s.

[0064] After the coating was completed, compressed air was introduced into the chamber to return it to normal pressure. The coated silicon wafers, printed circuit boards, and black ink glossy plate samples were then removed. The silicon wafers were placed on a rotating holder in three layers, designated A, B, and C, from top to bottom, and the coating thickness and water contact angle were tested. The results are shown in Table 1. The printed circuit boards were placed on a rotating holder in three layers, designated A, B, and C, from top to bottom, and the results of a 20.5V acid sweat immersion test are shown in Table 1. The black ink glossy plate samples were placed on a rotating holder in three layers, designated A, B, and C, from top to bottom, and the results of a black ink glossy plate bonding strength test are shown in Table 1. Example 3

[0065] Parylene C powder and 3-aminopropyltriethoxysilane monomer were charged into their respective supply areas, and silicon wafer, printed circuit board, and black ink gloss plate samples were placed on a rotating holder in a vacuum growth chamber. The rotating holder was turned on and rotated, and the chamber was evacuated to 10 mTorr. Helium gas was introduced at a flow rate of 40 sccm and controlled to stabilize the pressure at 80 mTorr. The chamber temperature was 30°C.

[0066] A continuous plasma discharge was initiated. In this pretreatment stage, the discharge power was 180 W and the discharge continued for 300 seconds. After the surface pretreatment of the silicon wafer, printed circuit board, and black ink gloss plate samples was completed, the discharge was terminated.

[0067] Next, 3-aminopropyltriethoxysilane monomer was introduced into the vaporization chamber, vaporized at a vaporization temperature of 90 °C, and then introduced into the chamber. Pulse plasma discharge was initiated, and plasma chemical vapor deposition was performed. The pulse duty ratio was 8%, the pulse frequency was 50 Hz, the pulse discharge power was 200 W, the flow rate of the monomer introduced into the vaporization chamber was 480 μL / min, and the reaction time was 600 s.

[0068] The discharge was terminated, the monomer supply and helium gas were stopped, and the chamber pressure was controlled to 20 mTorr. The Parylene C powder was heated to 170°C in the sublimation chamber to be sublimated, then introduced into the decomposition chamber and decomposed at a temperature of 690°C. It was then introduced into the chamber and deposited for 4 hours. The undeposited raw material was adsorbed in a cold trap to prevent it from entering the vacuum pump.

[0069] Next, the valve connecting the parylene decomposition furnace and the chamber was closed, and He gas was again introduced at a flow rate of 40 sccm. The pressure was controlled to 100 mTorr. After stabilization, hydroxyethyl methacrylate monomer was introduced into the vaporization chamber, vaporized at a vaporization temperature of 110°C, and introduced into the chamber. Pulse plasma discharge was initiated, and plasma-enhanced chemical vapor deposition was performed. The pulse duty ratio was 80%, the frequency was 50 Hz, the discharge power was 300 W, the monomer flow rate was 300 μL / min, and the reaction time was 3600 s.

[0070] After the coating was completed, compressed air was introduced into the chamber to return it to normal pressure. The coated silicon wafers, printed circuit boards, and black ink glossy plate samples were then removed. The silicon wafers were placed on a rotating holder in three layers, designated A, B, and C, from top to bottom, and the coating thickness and water contact angle were tested. The results are shown in Table 1. The printed circuit boards were placed on a rotating holder in three layers, designated A, B, and C, from top to bottom, and the results of a 20.5V acid sweat immersion test are shown in Table 1. The black ink glossy plate samples were placed on a rotating holder in three layers, designated A, B, and C, from top to bottom, and the results of a black ink glossy plate bonding strength test are shown in Table 1. Comparative Example 1

[0071] Parylene C powder was loaded into the supply area, and silicon wafer, printed circuit board, and black ink gloss plate samples were placed on a rotating holder in a vacuum growth chamber. The rotating holder was turned on and rotated, and the chamber was evacuated to 10 mTorr, and the chamber temperature was 30°C.

[0072] The chamber pressure was controlled at 20 mTorr, and the Parylene C powder was heated to 170°C in the sublimation chamber to be sublimated. It was then introduced into the decomposition chamber and decomposed at a temperature of 690°C. It was then introduced into the chamber and deposited for 4 hours. The undeposited raw material was adsorbed in a cold trap to prevent it from entering the vacuum pump.

[0073] After the coating was completed, compressed air was introduced into the chamber to return it to normal pressure. The coated silicon wafers, printed circuit boards, and black ink glossy plate samples were then removed. The silicon wafers were placed on a rotating holder in three layers, designated A, B, and C, from top to bottom, and the coating thickness and water contact angle were tested. The results are shown in Table 1. The printed circuit boards were placed on a rotating holder in three layers, designated A, B, and C, from top to bottom, and the results of a 20.5V acid sweat immersion test are shown in Table 1. The black ink glossy plate samples were placed on a rotating holder in three layers, designated A, B, and C, from top to bottom, and the results of a black ink glossy plate bonding strength test are shown in Table 1. Comparative Example 2

[0074] Parylene N powder was loaded into the supply area, and silicon wafers, printed circuit boards, and black ink gloss plate samples were placed on a rotating holder in a vacuum growth chamber. The rotating holder was turned on and rotated, and the chamber was evacuated to 10 mTorr, and the chamber temperature was 30 °C.

[0075] The chamber pressure was controlled at 20 mTorr, and the parylene N powder was heated to 150 °C in the sublimation chamber to be sublimated. It was then introduced into the decomposition chamber and decomposed at a temperature of 650 °C. It was then introduced into the chamber and deposited for 4 h. The undeposited raw material was adsorbed in a cold trap to prevent it from entering the vacuum pump.

[0076] After the coating was completed, compressed air was introduced into the chamber to return it to normal pressure. The coated silicon wafers, printed circuit boards, and black ink glossy plate samples were then removed. The silicon wafers were placed on a rotating holder in three layers, designated A, B, and C, from top to bottom, and the coating thickness and water contact angle were tested. The results are shown in Table 1. The printed circuit boards were placed on a rotating holder in three layers, designated A, B, and C, from top to bottom, and the results of a 20.5V acid sweat immersion test are shown in Table 1. The black ink glossy plate samples were placed on a rotating holder in three layers, designated A, B, and C, from top to bottom, and the results of a black ink glossy plate bonding strength test are shown in Table 1. Comparative Example 3

[0077] Parylene C powder was loaded into the supply area, and silicon wafer, printed circuit board, and black ink gloss plate samples were placed on a rotating holder in a vacuum growth chamber. The rotating holder was turned on and rotated, and the chamber was evacuated to 10 mTorr. Helium gas was introduced at a flow rate of 40 sccm and controlled to stabilize the pressure at 80 mTorr. The chamber temperature was 30°C.

[0078] The plasma continuous discharge was initiated at a discharge power of 180 W and continued for 300 seconds. After surface pretreatment of the silicon wafer, printed circuit board, and black ink gloss plate samples, the discharge was terminated, the helium gas was stopped, and the chamber pressure was controlled at 20 mTorr. The Parylene C powder was heated to 170°C in the sublimation chamber to sublimate, then introduced into the decomposition chamber and decomposed at 690°C. It was then introduced into the deposition chamber and deposited for 4 hours. The remaining material was adsorbed in a cold trap to prevent it from entering the vacuum pump.

[0079] After the coating was completed, compressed air was introduced into the chamber to return it to normal pressure. The coated silicon wafers, printed circuit boards, and black ink glossy plate samples were then removed. The silicon wafers were placed on a rotating holder in three layers, designated A, B, and C, from top to bottom, and the coating thickness and water contact angle were tested. The results are shown in Table 1. The printed circuit boards were placed on a rotating holder in three layers, designated A, B, and C, from top to bottom, and the results of a 20.5V acid sweat immersion test are shown in Table 1. The black ink glossy plate samples were placed on a rotating holder in three layers, designated A, B, and C, from top to bottom, and the results of a black ink glossy plate bonding strength test are shown in Table 1.

[0080] [Table 1] Test results for Examples 1 to 3 and Comparative Examples 1 to 3 JPEG2025539603000017.jpg109150

[0081] The results in Table 1 above show that, compared to Comparative Examples 1 to 3, Examples 1 to 3 all achieved 20.5V acidic sweat immersion times of over 100 hours, demonstrating the parylene coating's excellent acid resistance. However, Examples 1 to 3 also demonstrated superior adhesion to black ink glossy plates, indicating that the formation of a plasma-polymerized coating of 3-aminopropyltriethoxysilane between the parylene coating and the substrate significantly improved the adhesion between the parylene coating and the substrate. The results in Examples 2 and 3 also demonstrate that the use of a hydrophobic or hydrophilic monomer plasma can effectively form a hydrophobic or hydrophilic coating on the parylene coating, thereby significantly expanding the range of applications for parylene coatings.

[0082] Although the present disclosure has been disclosed as above, the present disclosure is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present disclosure. Therefore, the scope of protection of the present disclosure should be based on the scope defined by the claims.

Claims

1. A composite coating comprising Coating I and Coating II, The coating I is a plasma polymerized coating formed by contacting a substrate with a plasma containing a monomer α, the monomer α having the structure shown in formula (1): （１） In formula (1), R 1 is a vinyl group or C 1 ~C 10 a substituted alkyl group represented by the formula: wherein the substituent of the substituted alkyl group includes at least one of a halogen atom, an alkenyl group, an alkynyl group, a hydrocarbyloxy group, an amino group, an epoxy group, an acyloxy group, an amido group, a hydroxy group, or a mercapto group; R 2 , R 3 and R 4 are each independently a halogen atom, C 1 ~C 10 an alkoxy group of C 1 ~C 10 a substituted alkoxy group of C 1 ~C 10 or an acyloxy group of C 1 ~C 10 substituted acyloxy groups selected from the group consisting of: A composite coating, wherein the coating II is a parylene coating formed on the coating I by vacuum vapor deposition.

2. The R 1 is a vinyl group, a glycidyloxypropyl group, an acryloyloxypropyl group, a methacryloyloxypropyl group, an N-(β-aminoethyl)-γ-aminopropyl group, an N-(β-aminoethyl)-γ-aminopropyl-methyl group, a chloropropyl group, a mercaptopropyl group, a hydroxypropyl group, or an aminopropyl group, and 2 , R 3 and R 4 2. The composite coating of claim 1, wherein is a chlorine atom, a methoxy group, an ethoxy group, or a methoxyethoxy group.

3. The monomer α may be vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane, γ-glycidyloxypropyl-trimethoxysilane, γ-glycidyloxypropyl-triethoxysilane, 3-(acryloyloxy)propyltrimethoxysilane, γ-methacryloyloxypropyl-trimethoxysilane, γ-methacryloyloxypropyl-triethoxysilane, N-(β-aminoethyl)-γ-aminopropyl-methyl-trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl-methyl-trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl-methyl-trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl-methyl-trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl-methyl-trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl-methyl-triethoxy ...

3. The composite coating of claim 2, wherein the silane is selected from at least one of N-(β-aminoethyl)-γ-aminopropyl-triethoxysilane, N-(β-aminoethyl)-γ-aminopropyl-trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl-triethoxysilane, γ-chloropropyl-trimethoxysilane, γ-chloropropyl-triethoxysilane, γ-mercaptopropyl-trimethoxysilane, γ-mercaptopropyl-triethoxysilane, γ-aminopropyl-trimethoxysilane, or γ-aminopropyl-triethoxysilane.

4. 4. The composite coating of claim 3, wherein the monomer α is γ-aminopropyltriethoxysilane.

5. 2. The composite coating of claim 1, further comprising a coating III that is a plasma-polymerized hydrophobic coating or a plasma-polymerized hydrophilic coating formed by contacting the coating II with a plasma containing monomer β.

6. 6. The composite coating of claim 5, wherein the monomer β has a structure represented by the following formula (2): （２） In formula (2), R 5 is a bond, C 1 ~C 4 or an alkylene group of C 1 ~C 4 wherein Y is a halogen atom, a hydrogen atom, a hydroxy group, or a structure represented by the following formula (3) or (4), and n is an integer of 1 to 12. （３） （４） In formula (3), R 6 , R 7 and R 8 are each independently a hydrogen atom, a halogen atom, or C 1 ~C 4 or an alkyl group of C 1 ~C 4 X is a bond or an ester bond; In formula (4), R 9 , R 10 and R 11 are each independently a hydrogen atom, C 1 ~C 4 alkyl group of C 1 ~C 4 halogenated alkyl groups of C 1 ~C 4 or an alkoxy group of C 1 ~C 4 The halogenated alkoxy groups are selected from the group consisting of:

7. 7. The composite coating of claim 6, wherein the monomer β has a structure represented by the following formula (5): （５） In formula (5), m is an integer of 0 to 4.

8. The R 6 , R 7 and R 8 are each independently selected from a hydrogen atom or a methyl group; m is an integer from 0 to 2; and n is an integer from 1 to 10.

9. 9. The composite coating of claim 8, wherein the monomer β is 2-perfluorohexylethyl acrylate.

10. 6. The composite coating of claim 5, wherein the monomer β has a structure represented by the following formula (6): （６） In formula (6), R 12 , R 13 and R 14 are each independently a hydrogen atom, a halogen atom, or C 1 ~C 4 or an alkyl group of C 1 ~C 4 and R 15 is a bond, C 1 ~C 4 or an alkylene group of C 1 ~C 4 is a halogenated alkylene group of the formula R 16 , R 17 and R 18 are each independently a hydrogen atom, C 1 ~C 4 alkyl group of C 1 ~C 4 halogenated alkyl groups of C 1 ~C 4 or an alkoxy group of C 1 ~C 4 and Y is a bond or an oxygen atom.

11. The composite coating according to claim 5 , wherein the monomer β has a structure represented by the following formula (7): （７） In formula (7), R 19 is C 1 ~C 4 an amide group of C 1 ~C 4 a substituted alkoxy group of C 1 ~C 4 or a substituted alkyl group of C 1 ~C 4 and R 20 , R 21 and R 22 are each independently a hydrogen atom, C 1 ~C 4 an amide group of C 1 ~C 4 a substituted alkoxy group of C 1 ~C 4 a substituted alkyl group of C 1 ~C 4 or a substituted ester group of C 1 ~C 4 The hydrocarbyl groups are selected from the group consisting of: Said C 1 ~C 4 a substituted alkoxy group of C 1 ~C 4 and C 1 ~C 4 The substituent of the substituted ester group is a hydroxy group, a carboxy group or an amino group.

12. The R 19 is C 1 ~C 4 and R 20 , R 21 and R 22 12. The coating of claim 11, wherein each is independently selected from a hydrogen atom or a methyl group.

13. 12. The coating of claim 11, wherein the monomer β is selected from at least one of acrylic acid, methacrylic acid, 3,3-dimethylacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, 1-buten-3-ol, 2-butene-1,4-diol, 3-penten-2-ol, cis-3-hexen-1-ol, methallyl alcohol, 2,7-octadien-1-ol, N-t-butylacrylamide, glycerol dimethacrylate, N,N-diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, or N,N-dimethylacrylamide.

14. 6. The composite coating according to claim 5, wherein the coating III is a plasma-polymerized hydrophobic coating or a plasma-polymerized hydrophilic coating formed by contacting the coating II with a plasma containing a monomer β and a monomer δ, wherein the monomer δ has a structure represented by the following formula (8): （８） In formula (8), R 24 , R 25 , R 26 , R 27 , R 28 and R 29 are each independently a hydrogen atom, C 1 ~C 10 or an alkyl group of C 1 ~C 10 and R 23 is the linking site.

15. 15. The composite coating of claim 14, wherein the monomer δ has a structure shown in formula (9): （９） In formula (9), R 30 is C 2 ~C 10 or an alkylene group of C 2 ~C 10 and a is an integer of 1 to 10.

16. The R 24 , R 25 , R 26 , R 27 , R 28 and R 29 16. The composite coating of claim 15, wherein each is independently selected from a hydrogen atom or a methyl group, and a is an integer from 1 to 4.

17. 17. The composite coating of claim 16, wherein the monomer δ is selected from at least one of 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, or neopentyl glycol dimethacrylate.

18. A method for producing a composite coating according to any one of claims 1 to 17, comprising the steps of: providing a substrate, placing the substrate in a vacuum growth chamber, introducing a gaseous monomer α into the vacuum growth chamber, generating a plasma discharge, and plasma polymerizing the monomer α on the substrate surface to form the coating I; and Sublimating and decomposing parylene powder and then introducing it into the vacuum growth chamber to form a coating II on the coating I; 1. A method for producing a composite coating, comprising:

19. 20. The method for producing a composite coating according to claim 18, further comprising introducing gaseous monomer β, or gaseous monomer β and monomer δ, into the vacuum growth chamber, generating a plasma discharge, and plasma polymerizing the gaseous monomer β and the gaseous monomer δ on the surface of coating II to form coating III.

20. A device, characterized in that at least part of its surface is provided with a composite coating according to any one of claims 1 to 17.

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