Composite Coating, Manufacturing Method, and Device

Abstract

A specific embodiment of the present invention provides a composite coating, which has a base layer formed from a plasma of a monomer of a multifunctional ester having an epoxy structure and an ester-based coupling agent, and a corrosion-resistant layer formed from a plasma of an unsaturated ester-based monomer having an aromatic ring and an ester-based coupling agent, and the coating has high bonding strength with the substrate and strong corrosion resistance.

Description

[Technical field]

[0001] cross reference This application claims priority from a Chinese patent application with application number 202110242082.0, titled "Composite Coating, Manufacturing Method and Device," filed with the State Intellectual Property Office of the People's Republic of China on March 4, 2021, the entire contents of which are incorporated herein by reference.

[0002] The present invention is in the field of plasma chemistry, and more particularly, relates to plasma polymerized composite coatings and methods for their preparation. [Background technology]

[0003] Various products, such as electronic or electrical devices and components, metal products, etc., are very sensitive to damage caused by contamination with liquids, especially water. For example, when electronic or electrical devices are used normally or accidentally exposed to liquids, short circuits between electronic elements may occur, causing irreparable damage to circuit boards, electronic chips, etc. Organic polymer coatings can effectively protect the surfaces of various materials, and among the methods of organic polymer coating, the vapor deposition method for making polymer protective coatings on the surface of a substrate is the mainstream method, which has the characteristics of being economical, applicable, easy to operate, etc., and in particular, plasma chemical vapor deposition uses plasma to activate reactive monomer gases and deposit them on the surface of a substrate. This method is suitable for various substrates, and the deposited polymer protective coating is uniform, and can effectively deposit ultra-thin, transparent, insulating anti-aging plasma polymerization coatings, which can selectively protect electronic components, especially printed circuit boards. At present, plasma protective layers have disadvantages such as poor bonding strength with the substrate, easy peeling, and unstable corrosion resistance. Summary of the Invention [Problem to be solved by the invention]

[0004] A specific embodiment of the present invention is to provide a high bonding strength, strong corrosion resistant composite coating, manufacturing method and device, the specific scheme is as follows:

[0005] A composite coating comprising Coating I and Coating II deposited on a substrate, said coating I being a plasma polymerized coating formed by a plasma containing monomer α and monomer β; the coating II is a plasma polymerized coating formed on the coating I by contacting the coating I with a plasma comprising monomer γ and monomer δ; The structure of the monomer α is shown in formula (1-1): [ka] (wherein R1 is selected from CH or a cycloalkyl group having 3 to 8 carbon atoms; R2, R3, and R4 are each independently selected from a bond or an alkylene group having 1 to 6 carbon atoms; and when R2 and R3 are both bonds, they are not bonded to the same carbon atom; A is a linking moiety; and B includes a carbon-carbon unsaturated bond or an epoxy structure.) The structure of the monomer β is shown in formula (2-1): [ka] (wherein S1 contains one or more of -OC(O)- or -C(O)-O-; R5, R6, R7, R8, R9 and R 10 are each independently a hydrogen atom, a halogen atom, or a C 10 or C1-C 10 The halogen atom-substituted alkyl group is selected from the group consisting of: The structure of the monomer γ is shown in formula (3-1): [ka] (wherein Ar is a structure having an aromatic ring, T is -OC(O)- or -C(O)-O-, X is a linking moiety, Y is a linking moiety, and R11 , R 12 and R 13 are each independently a hydrogen atom, a halogen atom, or a C 10 or C1-C 10 The halogen atom-substituted alkyl group is selected from the group consisting of: The structure of the monomer δ is shown in formula (4-1), [ka] (wherein S2 contains one or more -OC(O)- or -C(O)-O-; R 14 , R 15 , R 16 , R 17 , R 18 and R 19 are each independently a hydrogen atom, a halogen atom, or a C 10 or C1-C 10 The halogen atom-substituted alkyl group is selected from the group consisting of:

[0006] Optionally, said A is -OC(O)- or -C(O)-O-.

[0007] Optionally, the structure of the monomer α is shown in formula (1-2): [ka] (where R 20 , R 21 and R 22 are each independently a hydrogen atom, a halogen atom, or a C 10 or C1-C 10 The halogen atom-substituted alkyl group is selected from the group consisting of:

[0008] Optionally, said R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R19 are each independently selected from a hydrogen atom or a methyl group.

[0009] Optionally, said R 20 , R 21 and R 22 are each independently selected from a hydrogen atom or a methyl group.

[0010] Optionally, the monomer a is selected from one or more of glycidyl methacrylate, tetrahydrofurfuryl acrylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, 1,2-epoxy-4-vinylcyclohexane, bis(2,3-epoxycyclopentyl)ether, 2,3-epoxycyclopentyl cyclopentyl ether, vinylcyclohexene dioxide, diisoprene dioxide, or bis((3,4-epoxycyclohexyl)methyl)adipate.

[0011] Optionally, S1 and / or S2 contain two -OC(O)- or -C(O)-O-.

[0012] Optionally, the S1 structure is shown in formula (2-2): [ka] (where R 23 is C2~C 10 or an alkylene group of C2 to C 10 and y is an integer of 0 to 10.

[0013] Optionally, the monomer β 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, neopentyl glycol dimethacrylate, methacrylic anhydride, diprop-2-enyl 2-methylene succinate, diprop-2-enyl 2-benzylidene malonate, or diethyl diallyl malonate.

[0014] Optionally, the X1 structure is shown in formula (3-2): [ka] (where X 11 is a bond, -O- or -C(O)-, and X 12 is a bond, C1~C 10 or an alkylene group of C1 to C 10 is a halogen atom-substituted alkylene group represented by the formula: The Y1 is a bond, C1 to C 10 or an alkylene group of C1 to C 10 It is a halogen atom-substituted alkylene group.

[0015] Optionally, said Ar is a benzene ring structure or a substituted benzene ring structure.

[0016] Optionally, the monomer γ structure is shown in formula (3-3): [ka] (wherein T2 is -OC(O)- or -C(O)-O-, X2 is a linking moiety, and Y2 is a linking moiety; R 24 , R 25 and R 26 are each independently a hydrogen atom, a halogen atom, or a C 10 or C1-C 10The halogen atom-substituted alkyl group is selected from the group consisting of:

[0017] Optionally, the structure of X2 is shown in formula (3-4): [ka] (where X 21 is a bond, -O- or -C(O)-, and X 22 is a bond, C1~C 10 or an alkylene group of C1 to C 10 is a halogen atom-substituted alkylene group represented by the formula: The Y2 is a bond, C1 to C 10 or an alkylene group of C1 to C 10 It is a halogen atom-substituted alkylene group.

[0018] Optionally, said R 24 , R 25 and R 26 are each independently selected from a hydrogen atom or a methyl group.

[0019] Optionally, said monomer γ is selected from at least one of 2-phenoxyethyl acrylate, phenyl acrylate, diallyl terephthalate, or phenyl methacrylate.

[0020] Optionally, the S2 structure is shown in formula (4-2): [ka] (where R 27 is C2~C 10 or an alkylene group of C2 to C 10 and z is an integer of 0 to 10.

[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, neopentyl glycol dimethacrylate, methacrylic anhydride, diprop-2-enyl 2-methylene succinate, diprop-2-enyl 2-benzylidene malonate, or diethyl diallyl malonate.

[0022] Optionally, the composite coating further comprises a coating III that is a plasma polymerized coating formed on coating II by contacting coating II with a plasma comprising monomer ε; The structure of the monomer ε is shown in formula (5-1). [ka] (where Z is a linking moiety and R 28 , R 29 and R 30 are each independently a hydrogen atom, a halogen atom, or a C 10 or a hydrocarbon group of C1 to C 10 and x is an integer of 1 to 20.

[0023] Optionally, Z is a bond, a C1-C4 alkylene group or a C1-C4 alkylene group having a substituent, and x is 5 or more.

[0024] Optionally, said R 28 , R 29 and R 30 are each independently selected from a hydrogen atom or a methyl group.

[0025] Optionally, the monomer ε is selected from one or more of 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl methacrylate, 2-(perfluorodecyl)ethyl methacrylate, 2-(perfluorohexyl)ethyl methacrylate, 2-(perfluorododecyl)ethyl acrylate, 2-(perfluorooctyl)ethyl acrylate, 1H,1H,2H,2H-perfluorooctyl acrylate, 2-(perfluorobutyl)ethyl acrylate, (2H-perfluoropropyl)-2-acrylate, or (perfluorocyclohexyl)methyl acrylate.

[0026] Optionally, the composite coating has a thickness of 50 to 300 nm.

[0027] Optionally, the molar ratio of monomer α to monomer β is between 1:5 and 5:1.

[0028] Optionally, the molar ratio of monomer γ to monomer δ is between 3:10 and 10:3.

[0029] Optionally, the substrate is a metal, plastic, fabric, glass, electrical component, optical device, or electrical component.

[0030] A method for producing a composite coating according to any one of the above, comprising the steps of: Providing a substrate, placing the substrate in a plasma reaction chamber, evacuating to 20-200 mTorr, and introducing an inert gas, He, Ar, O2 or some mixed gas; Introducing a mixed monomer vapor of monomer α and monomer β into the reaction chamber and initiating a plasma discharge to form a plasma polymerized coating I; and A method for producing a composite coating, comprising: introducing a mixed monomer vapor of monomer γ and monomer δ into a reaction chamber and initiating a plasma discharge to form a plasma polymerized coating II on the coating I.

[0031] Optionally, monomer ε vapor is introduced into the reaction chamber and a plasma discharge is initiated to form a plasma polymerized coating III on coating II.

[0032] Optionally, the plasma is a pulsed plasma.

[0033] Optionally, the pulsed plasma is generated by applying a pulsed voltage discharge, with a pulse power of 50W-500W, a pulse frequency of 25Hz-85kHz, a pulse duty ratio of 5%-85%, and a plasma discharge time of 100s-36000s.

[0034] A device, at least a portion of whose surface has a composite coating according to any one of the preceding claims.

[0035] In a specific embodiment of the composite coating of the present invention, the coating formed by plasma of a multifunctional monomer having an epoxy structure and a monomer of an ester coupling agent is used as the underlayer, and the coating formed by plasma of an unsaturated ester monomer having an aromatic ring and an ester coupling agent is used as the anticorrosive layer. The underlayer is beneficial for tight bonding between the substrate and the anticorrosive layer and for improving the density of the composite coating. The anticorrosive layer has good stability of the aromatic ring, which allows the polymer to have relatively good hardness and heat resistance, and has improved hydrophobicity, reduced water solubility, and contains ester groups, which can form hydrogen bonding force and have better adhesion, so that the composite coating can have good protective performance when it is a very thin coating. In addition, the multifunctional monomer having an epoxy structure adopts a multifunctional ester having an epoxy structure, especially an acrylate having an epoxy structure, so that the entire composite coating has better protective performance, and further, the protective performance of the composite coating can be further improved by forming a fluorine-containing hydrophobic layer on the anticorrosive layer. [Brief description of the drawings]

[0036] [Figure 1]FIG. 1 shows Tafel plots obtained by carrying out electrochemical tests on the coated and uncoated Mg sheets in Example 3. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0037] In a specific embodiment of the composite coating of the present invention, the composite coating comprises a coating I and a coating II deposited on a substrate, said coating I being a plasma polymerized coating formed by a plasma containing monomer α and monomer β; the coating II is a plasma polymerized coating formed on the coating I by contacting the coating I with a plasma comprising monomer γ and monomer δ; The structure of the monomer α is shown in formula (1-1): [ka] (wherein R1 is selected from CH or a cycloalkyl group having 3 to 8 carbon atoms; R2, R3, and R4 are each independently selected from a bond or an alkylene group having 1 to 6 carbon atoms; and when R2 and R3 are both bonds, they are not bonded to the same carbon atom; A is a linking moiety; and B includes a carbon-carbon unsaturated bond or an epoxy structure.) The structure of the monomer β is shown in formula (2-1): [ka] (wherein S1 contains one or more of -OC(O)- or -C(O)-O-; R5, R6, R7, R8, R9 and R 10 are each independently a hydrogen atom, a halogen atom, or a C 10 or C1-C 10 The halogen atom-substituted alkyl group is selected from the group consisting of: The structure of the monomer γ is shown in formula (3-1): [ka] (wherein Ar is a structure having an aromatic ring, T is -OC(O)- or -C(O)-O-, X is a linking moiety, Y is a linking moiety, and R 11 , R 12 and R 13 are each independently a hydrogen atom, a halogen atom, or a C 10 or C1-C 10 The halogen atom-substituted alkyl group is selected from the group consisting of: The structure of the monomer δ is shown in formula (4-1): [ka] (wherein S2 contains one or more -OC(O)- or -C(O)-O-; R 14 , R 15 , R 16 , R 17 , R 18 and R 19 are each independently a hydrogen atom, a halogen atom, or a C 10 or C1-C 10 The halogen atom-substituted alkyl group is selected from the group consisting of:

[0038] In the composite coating of a specific embodiment of the present invention, when R2 and R3 are both bonds, they are not bonded to the same carbon atom; specifically, when R1 is selected from CH, R2 and R3 are not bonds at the same time; when R1 is selected from a cycloalkyl group, R2 and R3 share two carbon atoms with R1, or R2 and R3 share one carbon atom with R1, and R2 and R3 are not bonds at the same time.

[0039] In the composite coating of a specific embodiment of the present invention, Coating I is deposited on a substrate by plasma chemical vapor deposition from a polyfunctional monomer α having an epoxy structure as shown in formula (1-1) and an ester coupling agent monomer β as shown in formula (1-2), and can tightly bond the substrate and the anticorrosive layer of the composite coating. Coating II is deposited on Coating I by plasma chemical vapor deposition from an unsaturated ester monomer γ having an aromatic ring as shown in formula (1-3) and an ester coupling agent monomer δ as shown in formula (1-4), and the aromatic ring contained therein has good stability, and can provide the polymer coating with relatively good hardness and heat resistance, and also has improved hydrophobicity and reduced water solubility. In addition, since it contains an ester group, it can combine with the ester bond of Coating I to form a hydrogen bond, and has good adhesion, so that the composite coating can have good protective performance even when it is a very thin coating.

[0040] In the composite coating of the specific embodiment of the present invention, in some specific embodiments, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 are each independently selected from a hydrogen atom or a methyl group.

[0041] In the composite coating of the specific embodiment of the present invention, in some specific embodiments, R1 is selected from a C3-C8 cycloalkyl group, such as cyclopentyl or cyclohexyl, and R2 and R3 share two carbon atoms with R1. R2, R3, and R4 are each independently selected from a bond or a C1-C6 alkylene group, and the alkylene group includes a straight chain alkylene group, such as a methylene group, an ethylene group, a propylene group, or a butylene group, or a branched chain-containing alkylene group, such as an isopropylene group or an isobutylene group.

[0042] In the composite coating of the specific embodiment of the present invention, in some specific embodiments, in formula (1-1), B is a carbon-carbon unsaturated double bond or a carbon-carbon unsaturated triple bond or an epoxy structure, so that the denseness of the coating can be formed according to the epoxy structure in the structure. In some specific embodiments, A is -OC(O)- or -C(O)-O-, and the structure of the monomer α is shown in formula (1-2): [ka] Here, R 20 , R 21 and R 22 are each independently a hydrogen atom, a halogen atom, or a C 10 or C1-C 10 The composite coating obtained by using the monomer α of this structure has better protective performance. In some specific embodiments, the R 20 , R 21 and R 22 are each independently selected from a hydrogen atom or a methyl group. The alkyl group may be a straight-chain alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a branched-chain-containing alkyl group such as an isopropyl group or an isobutyl group.

[0043] In the composite coating of a specific embodiment of the present invention, the monomer α is selected from the group consisting of glycidyl methacrylate (CAS number: 106-91-2), tetrahydrofurfuryl acrylate (CAS number: 2399-48-6), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (CAS number: 2386-87-0), 3,4-epoxycyclohexylmethyl acrylate (CAS number: 64630-63-3), 3,4-epoxycyclohexylmethyl meth ... S number: 82428-30-6), 1,2-epoxy-4-vinylcyclohexane (CAS number: 106-86-5), bis(2,3-epoxycyclopentyl) ether (CAS number: 2386-90-5), 2,3-epoxycyclopentyl cyclopentyl ether, vinylcyclohexene dioxide (CAS number: 106-87-6), diisoprene dioxide or bis((3,4-epoxycyclohexyl)methyl)adipate (CAS number: 3130-19-6).

[0044] In the composite coating of specific embodiments of the present invention, in some specific embodiments, S1 contains two -OC(O)- or -C(O)-O-, i.e., S1 contains two -OC(O)-, two -C(O)-O-, or one each of -OC(O)- and -C(O)-O-.

[0045] In the composite coating of the specific embodiment of the present invention, in some specific embodiments, S1 has a structure shown in formula (2-2). [ka] Here, R 23 is C2~C 10 or an alkylene group of C2 to C 10The alkylene group includes a linear alkylene group such as a methylene group, an ethylene group, a propylene group, or a butylene group, or a branched alkylene group such as an isopropylene group or an isobutylene group, and y is an integer of 0 to 10. Specifically, y is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0046] In the composite coating of a specific embodiment of the present invention, as specific non-limiting examples, the monomer β is 1,4-butanediol dimethacrylate (CAS number: 2082-81-7), 1,6-hexanediol dimethacrylate (CAS number: 6606-59-3), ethylene glycol dimethacrylate (CAS number: 97-90-5), diethylene glycol dimethacrylate (CAS number: 2358-84-1), triethylene glycol dimethacrylate (CAS number: 109-16-0), tetra ... At least one of ricol dimethacrylate (CAS number: 109-17-1), 1,3-butanediol dimethacrylate (CAS number: 1189-08-8), neopentyl glycol dimethacrylate (CAS number: 1985-51-9), methacrylic anhydride (CAS number: 760-93-0), diprop-2-enyl 2-methylene succinate, diprop-2-enyl 2-benzylidene malonate (CAS number: 52505-39-2) or diethyl diallyl malonate (CAS number: 3195-24-2) is selected.

[0047] In the composite coatings of specific embodiments of the present invention, in some specific embodiments, Ar is a benzene ring or a heteroaromatic ring having a substituent on the aromatic ring, and in other specific embodiments, Ar is a benzene ring or a heteroaromatic ring without a substituent on the aromatic ring.

[0048] In the composite coating of a specific embodiment of the present invention, X1 and Y1 are linking moieties, X1 is used to link the aromatic ring-containing structure Ar and the ester bond T1, and Y1 is used to link the ester bond T1 and the saturated carbon-carbon double bond. In some specific embodiments, X1 is a structure as shown in the following formula (3-2): [ka] Where X 11 is a bond, -O- or -C(O)-, and X 12 is a bond, C1~C 10 or an alkylene group of C1 to C 10 wherein Y1 is a bond, C1 to C 10 or an alkylene group of C1 to C 10 The alkylene group includes linear alkylene groups such as methylene, ethylene, propylene, or butylene, or branched alkylene groups such as isopropylene or isobutylene.

[0049] In the composite coating of the specific embodiment of the present invention, in some specific embodiments, the monomer γ has a structure shown in formula (3-3). [ka]

[0050] wherein T2 is -OC(O)- or -C(O)-O-, X2 is a linking moiety for bonding the benzene ring to the ester bond T2, and Y2 is a linking moiety for bonding the ester bond T2 to the carbon-carbon double bond; R 24 , R 25 and R 26 are each independently a hydrogen atom, a halogen atom, or a C 10 or C1-C 10The alkyl group includes a straight chain alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a branched chain-containing alkyl group such as an isopropyl group or an isobutyl group.

[0051] In the composite coating of the specific embodiment of the present invention, in some specific embodiments, the two substituents on the benzene ring in the structure shown in formula (3-3) are para-substituted, and in other embodiments, they may be ortho-substituted or meta-substituted.

[0052] In the composite coating of the specific embodiment of the present invention, in some specific embodiments, X2 is a structure shown in the following formula (3-4). [ka] where X 21 is a bond, -O- or -C(O)-, and X 22 is a bond, C1~C 10 or an alkylene group of C1 to C 10 wherein Y2 is a bond, C1 to C 10 or an alkylene group of C1 to C 10 The alkylene group includes linear alkylene groups such as methylene, ethylene, propylene, or butylene, or branched alkylene groups such as isopropylene or isobutylene.

[0053] In the composite coating of the specific embodiment of the present invention, in some specific embodiments, the R 24 , R 25 and R 26 are each independently selected from a hydrogen atom or a methyl group.

[0054] In the composite coating of a specific embodiment of the present invention, as a specific, non-limiting example, said monomer γ is selected from at least one of 2-phenoxyethyl acrylate (CAS number: 48145-04-6), phenyl acrylate (CAS number: 937-41-7), diallyl terephthalate (CAS number: 1026-92-2) or phenyl methacrylate (CAS number: 2177-70-0).

[0055] In the composite coating of specific embodiments of the present invention, in some specific embodiments, S2 contains two -OC(O)- or -C(O)-O-, i.e., S2 contains two -OC(O)-, two -C(O)-O-, or one each of -OC(O)- and -C(O)-O-.

[0056] In the composite coating of the specific embodiment of the present invention, in some specific embodiments, S2 has a structure shown in formula (4-2). [ka] Here, R 27 is C2~C 10 or an alkylene group of C2 to C 10 The alkylene group includes a linear alkylene group such as a methylene group, an ethylene group, a propylene group, or a butylene group, or a branched alkylene group such as an isopropylene group or an isobutylene group, and z is an integer of 0 to 10. Specifically, z is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0057] In the composite coating of a specific embodiment of the present invention, as a specific, non-limiting example, 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, neopentyl glycol dimethacrylate, methacrylic anhydride, diprop-2-enyl 2-methylene succinate, diprop-2-enyl 2-benzylidene malonate, or diethyl diallyl malonate.

[0058] In the composite coating of specific embodiments of the present invention, in some specific embodiments, the composite coating further comprises a coating III which is a plasma polymerized coating formed on the coating II by contacting the coating II with a plasma containing a monomer ε, the structure of the monomer ε being shown in formula (5-1). [ka] where Z is a linking moiety and R 28 , R 29 and R 30 are each independently a hydrogen atom, a halogen atom, or a C 10 or a hydrocarbon group of C1 to C 10 and x is an integer of 1 to 20.

[0059] In the composite coating of the specific embodiment of the present invention, Z is a linking site for connecting an ester bond to a perfluorocarbon alkyl group, and in some specific embodiments, Z is a bond, a C1-C4 alkylene group, or a C1-C4 alkylene group having a substituent. The alkylene group can be a straight chain alkylene group such as a methylene group, an ethylene group, a propylene group, or a butylene group, or a branched chain-containing alkylene group such as an isopropylene group or an isobutylene group, and the substituent can be, for example, a halogen atom, a hydroxy group, a carboxy group, or an ester group.

[0060] In the composite coating of specific embodiments of the present invention, in some specific embodiments, x is 4 or more, even 6 or more, and specifically, x is, for example, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20, which is beneficial for improving the hydrophobicity of the coating.

[0061] In the composite coating of a specific embodiment of the present invention, as specific non-limiting examples, the monomer ε is 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl methacrylate (CAS number: 16083-81-1), 2-(perfluorodecyl)ethyl methacrylate (CAS number: 2144-54-9), 2-(perfluorohexyl)ethyl methacrylate (CAS number: 2144-53-8), 2-(perfluorododecyl)ethyl acrylate (CAS number: 34395-24-9), The perfluorooctyl acrylate may be selected from one or more of 2-(perfluorooctyl)ethyl acrylate (CAS number: 27905-45-9), 1H,1H,2H,2H-perfluorooctyl acrylate (CAS number: 17527-29-6), 2-(perfluorobutyl)ethyl acrylate (CAS number: 52591-27-2), (2H-perfluoropropyl)-2-acrylate (CAS number: 59158-81-5) or (perfluorocyclohexyl)methyl acrylate (CAS number: 40677-94-9).

[0062] In the composite coating of the specific embodiment of the present invention, in some specific embodiments, the coating I is a plasma polymerized coating formed by a plasma containing monomer α and monomer β, the coating II is a plasma polymerized coating formed on the coating I by contacting the coating I with a plasma containing monomer γ and monomer δ, and the coating III is a plasma polymerized coating formed on the coating II by contacting the coating II with a plasma containing monomer ε. In other specific embodiments, the coating I may be a plasma polymerized coating formed by a plasma containing monomer α and monomer β plus other suitable monomers, the coating II may be a plasma polymerized coating formed on the coating I by contacting the coating I with a plasma containing monomer γ and monomer δ plus other suitable monomers, and the coating III may be a plasma polymerized coating formed on the coating II by a mixed monomer plasma of monomer ε and other suitable monomers, without affecting the overall coating performance of the coating I, coating II, or coating III.

[0063] In the composite coating of the specific embodiment of the present invention, in some specific embodiments, the thickness of the composite coating is 50-500 nm, and even under such an extremely thin thickness, the composite coating of the specific embodiment of the present invention can still maintain very good protective performance. In some specific embodiments, the substrate is a metal, and the thickness of the composite coating is 80-150 nm, specifically, for example, 80 nm, 90 nm, 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, or 150 nm. In some specific embodiments, the substrate is a circuit board, and the thickness of the composite coating is 200-300 nm, specifically, for example, 200 nm, 210 nm, 220 nm, 230 nm, 240 nm, 250 nm, 260 nm, 270 nm, 280 nm, 290 nm, or 300 nm.

[0064] In the composite coating of the specific embodiment of the present invention, in some specific embodiments, the molar ratio of the monomer α and the monomer β is between 1:5 and 5:1, specifically, for example, 1:5, 1:4, 1:3, 1:2.5, 1:2, 1:1.5, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 4:1 or 5:1, etc., and in other specific embodiments, it can be adjusted between other ratios according to the specific monomer situation and specific product protection requirements.

[0065] In the composite coating of the specific embodiment of the present invention, in some specific embodiments, the molar ratio of the monomer γ to the monomer δ is between 3:10 and 10:3, specifically, 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, etc., and in other specific embodiments, it can be adjusted between other ratios according to the specific monomer situation and specific product protection requirements.

[0066] In the composite coating of the specific embodiment of the present invention, in some specific embodiments, the substrate is a metal, specifically, for example, iron, magnesium, aluminum, copper or their alloys, and in other specific embodiments, the substrate is various plastics, fabrics, glass, electrical components or 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, it includes, but is 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 components may be resistors, capacitors, transistors, diodes, amplifiers, relays, transformers, batteries, fuses, integrated circuits, switches, LEDs, LED displays, piezoelectric elements, optoelectronic components, or antennas or oscillators, etc.

[0067] Particular embodiments of the present invention further provide a method for producing a composite coating according to any one of the above claims, the method comprising the steps of: Providing a substrate, placing the substrate in a plasma reaction chamber, evacuating to 20-200 mTorr, and introducing an inert gas, He, Ar, O2 or some mixed gas; Introducing a mixed monomer vapor of monomer α and monomer β into the reaction chamber and initiating a plasma discharge to form a plasma polymerized coating I; and introducing a mixed monomer vapor of monomer γ and monomer δ into the reaction chamber and initiating a plasma discharge to form a plasma polymerized coating II on the coating I.

[0068] The method for preparing the composite coating of the specific embodiment of the present invention further includes introducing monomer ε vapor into the reaction chamber and initiating a plasma discharge to form a plasma polymerized coating III on the coating II.

[0069] In the method for producing a composite coating according to a specific embodiment of the present invention, the monomer α, the monomer β, the monomer γ, the monomer δ, the monomer ε, the coating I, the coating II, and the coating III are as described above.

[0070] In the composite coating of the specific embodiment of the present invention, in order to further increase the bonding strength between the plasma coating and the substrate, in some specific embodiments, the substrate is a substrate pretreated by continuous wave plasma, and the specific conditions are, for example, under an inert gas atmosphere, the plasma discharge power is 50-500W, and may be, for example, 50W, 100W, 150W, 200w, 250w, 300w, 350w, 400w, 450w, 500w, etc. The continuous discharge time is 30-600s, and may be, for example, 30s, 50s, 100s, 200s, 300s, 400s, 500s, or 600s, etc. In some specific embodiments, the substrate is pretreated by heat, oxygen, or high-energy radiation.

[0071] In the method for preparing the composite coating of the specific embodiment of the present invention, in some specific embodiments, the plasma is a pulsed plasma, and the flow rate of the monomer is 50-500 μl / min, for example, 100 μl / min, 200 μl / min, 300 μl / min, or 400 μl / min. The vaporization temperature of the monomer may be 50° C.-120° C., for example, 50° C., 60° C., 70° C., 80° C., 90° C., 100° C., 110° C., 120° C., and vaporization occurs under vacuum conditions. The pulsed plasma is generated by applying a pulsed voltage discharge, and the pulsed power is 50W-500W, for example, 50W, 100W, 150W, 200w, 250w, 300w, 350w, 400w, 450w, or 500w. The pulse frequency is 25 Hz to 85 kHz, and may be, for example, 25 Hz, 30 Hz, 35 Hz, 40 Hz, 45 Hz, 50 Hz, 55 Hz, 60 Hz, 65 Hz, 70 Hz, 75 Hz, 80 Hz, or 85 Hz. The pulse duty ratio is 5% to 85%, and may be, for example, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, or 85%. The plasma discharge time is 100 s to 36,000 s, and may be, for example, 100 s, 200 s, 500 s, 1000 s, 2000 s, 3000 s, 4000 s, 5000 s, 6000 s, 7000 s, 8000 s, 9000 s, 10,000 s, 15,000 s, 20,000 s, 25,000 s, 30,000 s, or 36,000 s.

[0072] In the manufacturing method of the composite coating of the specific embodiment of the present invention, in some specific embodiments, the plasma discharge method may be any of the existing discharge methods, such as electrodeless discharge (e.g., radio frequency inductively coupled discharge, microwave discharge, etc.), single electrode discharge (e.g., corona discharge, plasma jet formed by a single electrode 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 the third electrode, etc.).

[0073] Specific embodiments of the present invention further provide a device, at least a portion of a surface of the device having a composite coating of any one of the above, and in some specific embodiments, some or all of the surface of the device is coated only with the protective coating described above.

[0074] The present invention will now be further described with reference to specific examples. Working Example Test method description

[0075] 20.5V Underwater Current Test: The test process is as follows: 1. The power supply supplies 20.5V voltage to the circuit board. 2. The circuit board is immersed in water. 3. The computer detects the current. 4. The failure time (current > 0.6mA) is recorded.

[0076] Salt spray test: Tested according to GB / T2423.18-2000 environmental test method for electrical and electronic products. Coating thickness test: Tested using Filmetrics F20-UV thin film thickness tester from the US.

[0077] Electrochemical test: The polarization curve in 3.6% NaCl neutral solution was tested using Shanghai Chenhua CHI660E C20704 electrochemical analyzer. The test conditions were: corrosion potential was minus 600mv to plus 600mv, scan speed was 0.00033mv / s, and scan time was 600s. EXAMPLES

[0078] The circuit board, Mg sheet, and Fe sheet were placed in the plasma chamber, the chamber was evacuated to 40 mTorr, helium gas was introduced at a flow rate of 60 sccm, and radio frequency plasma discharge was started to pretreat the substrate, and in this pretreatment stage, the discharge power was 150 W and the discharge lasted for 600 s.

[0079] Next, a mixed monomer of 1,4-butanediol diacrylate and tetrahydrofurfuryl acrylate (mass ratio 2:1) was introduced and vaporized at a vaporization temperature of 100°C, and then introduced into the chamber to perform plasma chemical vapor deposition. The mixed monomer flow rate was 150ul / min, and the plasma in the chamber was generated by a radio frequency discharge method, with the output method being pulse, discharge power 50W, frequency 45Hz, pulse duty ratio 25%, and discharge time 3600s.

[0080] Next, a mixed monomer of 1,6-hexanediol diacrylate and phenyl methacrylate (mass ratio 1:1) was introduced and vaporized at a vaporization temperature of 120°C, and then introduced into the chamber to perform plasma chemical vapor deposition. The mixed monomer flow rate was 100ul / min, and the plasma in the chamber was generated by a radio frequency discharge method, with the output method being pulse, discharge power 20w, frequency 25Hz, pulse duty ratio 65%, and discharge time 7200s.

[0081] Next, 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl methacrylate monomer was introduced and vaporized at a vaporization temperature of 120°C, and then introduced into the chamber to carry out plasma chemical vapor deposition. The monomer flow rate was 100ul / min, and the plasma in the chamber was generated by a radio frequency discharge method, with the output method being pulse, the discharge power being 180w, the frequency being 35Hz, the pulse duty ratio being 45%, and the discharge time being 7200s.

[0082] After coating was completed, compressed air was introduced into the chamber to return it to normal pressure. The circuit board was taken out and a 20.5V underwater electrical test was performed. The Mg sheet and Fe sheet samples were also subjected to a salt spray test. The test results are shown in Table 1. EXAMPLES

[0083] The circuit board, Mg sheet, and Fe sheet were placed in the plasma chamber, the chamber was evacuated to 8 mTorr, helium gas was introduced at a flow rate of 80 sccm, and radio frequency plasma discharge was started to pretreat the substrate, and in this pretreatment stage, the discharge power was 180 W and the discharge lasted for 300 s.

[0084] Next, a mixed monomer of triethylene glycol dimethacrylate and glycidyl methacrylate (mass ratio 2:1) was introduced and vaporized at a vaporization temperature of 180°C, and then introduced into the chamber to perform plasma chemical vapor deposition. The mixed monomer flow rate was 110 ul / min, and the plasma in the chamber was generated by a radio frequency discharge method, with the output method being pulse, discharge power 50 W, frequency 45 Hz, pulse duty ratio 45%, and discharge time 3000 s.

[0085] Next, a mixed monomer of 1,3-butanediol dimethacrylate and 2-phenoxyethyl acrylate (mass ratio 1:2) was introduced and vaporized at a vaporization temperature of 180°C, and then introduced into the chamber to perform plasma chemical vapor deposition. The mixed monomer flow rate was 250ul / min, and the plasma in the chamber was generated by a radio frequency discharge method, with the output method being pulse, discharge power 26w, frequency 85Hz, pulse duty ratio 25%, and discharge time 7200s.

[0086] Next, 2-(perfluorohexyl)ethyl methacrylate monomer was introduced and vaporized at a vaporization temperature of 120°C, and then introduced into the chamber to carry out plasma chemical vapor deposition. The monomer flow rate was 100ul / min, and the plasma in the chamber was generated by a radio frequency discharge method, with the output method being pulse, discharge power 90w, frequency 65Hz, pulse duty ratio 65%, and discharge time 1800s.

[0087] After coating was completed, compressed air was introduced into the chamber to return it to normal pressure. The circuit board was taken out and a 20.5V underwater electrical test was performed. The Mg sheet and Fe sheet samples were also subjected to a salt spray test. The test results are shown in Table 1. EXAMPLES

[0088] The circuit board, Mg sheet, and Fe sheet were placed in the plasma chamber, the chamber was evacuated to 80 mTorr, helium gas was introduced at a flow rate of 160 sccm, and radio frequency plasma discharge was started to pretreat the substrate, and in this pretreatment stage, the discharge power was 180 W and the discharge lasted for 300 s.

[0089] Next, a mixed monomer of 1,6-hexanediol diacrylate and 3,4-epoxycyclohexylmethylacrylate (mass ratio 2:1) was introduced and vaporized at a vaporization temperature of 180°C, and then introduced into the chamber to perform plasma chemical vapor deposition. The mixed monomer flow rate was 200ul / min, and the plasma in the chamber was generated by a radio frequency discharge method, with the output method being pulse, discharge power 50W, frequency 50Hz, pulse duty ratio 45%, and discharge time 2400s.

[0090] Next, a mixed monomer of 1,6-hexanediol diacrylate and phenyl acrylate (mass ratio 3:2) was introduced and vaporized at a vaporization temperature of 180°C, and then introduced into the chamber to perform plasma chemical vapor deposition. The mixed monomer flow rate was 280ul / min, and the plasma in the chamber was generated by a radio frequency discharge method, with the output method being pulse, discharge power 20w, frequency 50Hz, pulse duty ratio 15%, and discharge time 3000s.

[0091] Next, 2-(perfluorohexyl)ethyl methacrylate monomer was introduced and vaporized at a vaporization temperature of 120°C, and then introduced into the chamber to carry out plasma chemical vapor deposition. The monomer flow rate was 160ul / min, and the plasma in the chamber was generated by a radio frequency discharge method, with the output method being pulse, discharge power 180w, frequency 50Hz, pulse duty ratio 15%, and discharge time 2600s.

[0092] After coating was completed, compressed air was introduced to return the chamber to normal pressure. The circuit board was removed and a 20.5V underwater current test was performed, and a salt spray test was performed on the Mg sheet and Fe sheet samples, the test results of which are shown in Table 1. Electrochemical tests were performed on the coated and uncoated Mg sheets, and a Tafel plot was obtained as shown in Figure 1. The electrochemical parameters obtained by fitting this curve are shown in Table 2. EXAMPLES

[0093] The circuit board, Mg sheet, and Fe sheet were placed in the plasma chamber, the chamber was evacuated to 80 mTorr, helium gas was introduced at a flow rate of 120 sccm, and radio frequency plasma discharge was started to pretreat the substrate, and in this pretreatment stage, the discharge power was 500 W and the discharge lasted for 300 s.

[0094] Next, a mixed monomer of neopentyl glycol dimethacrylate and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (mass ratio 2:1) was introduced and vaporized at a vaporization temperature of 160°C, and then introduced into the chamber to perform plasma chemical vapor deposition. The mixed monomer flow rate was 300ul / min, and the plasma in the chamber was generated by a radio frequency discharge method, with the output method being pulse, discharge power 80W, frequency 25Hz, pulse duty ratio 50%, and discharge time 3600s.

[0095] Next, a mixed monomer of neopentyl glycol dimethacrylate and diallyl terephthalate (mass ratio 2:1) was introduced and vaporized at a vaporization temperature of 180°C, and then introduced into the chamber to perform plasma chemical vapor deposition. The mixed monomer flow rate was 400ul / min, and the plasma in the chamber was generated by a radio frequency discharge method, with the output method being pulse, discharge power 100w, frequency 45Hz, pulse duty ratio 45%, and discharge time 3600s.

[0096] Next, 2-(perfluorododecyl)ethyl acrylate monomer was introduced and vaporized at a vaporization temperature of 130°C, and then introduced into the chamber to carry out plasma chemical vapor deposition. The monomer flow rate was 150ul / min, and the plasma in the chamber was generated by a radio frequency discharge method, with the output method being pulse, discharge power 150w, frequency 35Hz, pulse duty ratio 50%, and discharge time 5400s.

[0097] After coating was completed, compressed air was introduced into the chamber to return it to normal pressure. The circuit board was taken out and a 20.5V underwater electrical test was performed. The Mg sheet and Fe sheet samples were also subjected to a salt spray test. The test results are shown in Table 1. Comparative Example 1

[0098] The circuit board, Mg sheet, and Fe sheet were placed in the plasma chamber, the chamber was evacuated to 80 mTorr, helium gas was introduced at a flow rate of 160 sccm, and radio frequency plasma discharge was started to pretreat the substrate, and in this pretreatment stage, the discharge power was 180 W and the discharge lasted for 300 s.

[0099] Next, a mixed monomer of 1,6-hexanediol diacrylate and phenyl acrylate (mass ratio 3:2) was introduced and vaporized at a vaporization temperature of 180°C, and then introduced into the chamber to perform plasma chemical vapor deposition. The mixed monomer flow rate was 280ul / min, and the plasma in the chamber was generated by a radio frequency discharge method, with the output method being pulse, discharge power 20w, frequency 50Hz, pulse duty ratio 15%, and discharge time 5400s.

[0100] Next, 2-(perfluorohexyl)ethyl methacrylate monomer was introduced and vaporized at a vaporization temperature of 120°C, and then introduced into the chamber to carry out plasma chemical vapor deposition. The monomer flow rate was 160ul / min, and the plasma in the chamber was generated by a radio frequency discharge method, with the output method being pulse, discharge power 180w, frequency 50Hz, pulse duty ratio 15%, and discharge time 2600s.

[0101] After coating was completed, compressed air was introduced into the chamber to return it to normal pressure. The circuit board was taken out and a 20.5V underwater electrical test was performed. The Mg sheet and Fe sheet samples were also subjected to a salt spray test. The test results are shown in Table 1. Comparative Example 2

[0102] The circuit board, Mg sheet, and Fe sheet were placed in a plasma chamber, the chamber was evacuated to 40 mTorr, helium gas was introduced at a flow rate of 60 sccm, and plasma discharge was started to pretreat the substrate. In this pretreatment stage, the discharge power was 150 W and the discharge continued for 600 s.

[0103] Next, a mixed monomer of 1,4-butanediol diacrylate and tetrahydrofurfuryl acrylate (mass ratio 2:1) was introduced and vaporized at a vaporization temperature of 100°C, and then introduced into the chamber to perform plasma chemical vapor deposition. The mixed monomer flow rate was 150ul / min, and the plasma in the chamber was generated by a radio frequency discharge method, with the output method being pulse, discharge power 50W, frequency 45Hz, pulse duty ratio 25%, and discharge time 3600s.

[0104] Next, 1,6-hexanediol diacrylate monomer was introduced and vaporized at a vaporization temperature of 120°C, and then introduced into the chamber to carry out plasma chemical vapor deposition. The monomer flow rate was 100ul / min, and the plasma in the chamber was generated by a radio frequency discharge method, with the output method being pulse, discharge power 20w, frequency 25Hz, pulse duty ratio 65%, and discharge time 7200s.

[0105] Next, 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl methacrylate monomer was introduced and vaporized at a vaporization temperature of 120°C, and then introduced into the chamber to carry out plasma chemical vapor deposition. The monomer flow rate was 100ul / min, and the plasma in the chamber was generated by a radio frequency discharge method, with the output method being pulse, the discharge power being 180w, the frequency being 35Hz, the pulse duty ratio being 45%, and the discharge time being 7200s.

[0106] After coating was completed, compressed air was introduced into the chamber to return it to normal pressure. The circuit board was taken out and a 20.5V underwater electrical test was performed. The Mg sheet and Fe sheet samples were also subjected to a salt spray test. The test results are shown in Table 1.

[0107] Performance test results of Examples 1 to 4 and Comparative Examples 1 and 2 [Table 1]

[0108] Electrochemical Parameter Results for Example 3 [Table 2]

[0109] From the performance test results of Examples 1 to 4 and Comparative Examples 1 to 2 in Table 1 above, Examples 1 to 4 have significantly better 20.5 V underwater current test times and salt spray test times than Comparative Examples 1 to 2, which shows that the composite coating in a specific embodiment of the present invention, in which a coating formed by monomer plasma of a polyfunctional ester having an epoxy structure and an ester coupling agent is used as an underlayer and a coating formed by plasma of an unsaturated ester monomer having an aromatic ring and an ester coupling agent is used as an anticorrosive layer, has excellent protective performance even under extremely thin coating. At the same time, Examples 1 to 3 have longer 20.5 V underwater current test times and salt spray test times than Example 4, which shows that when the polyfunctional ester having an epoxy structure in the underlayer is an enoate structure, the protective performance of the obtained composite coating is better.

[0110] From the electrochemical parameter results in Table 2 Example 3 above, it can be seen that the corrosion resistance of the uncoated magnesium sheet in 3.6% NaCl neutral solution is very poor, electrochemical corrosion occurs, the anodic reaction is the process in which magnesium loses electrons and dissolves, and the cathodic reaction is the process in which water gains electrons and generates hydrogen. Experiments have shown that the self-corrosion potential of the uncoated magnesium sheet is -1.385V, while the self-corrosion potential of the coated magnesium sheet is -1.128V, the corrosion potential is reduced by 23%, the corrosion resistance is improved, and at the same time, the current density of the coated magnesium sheet is 1.876e -9 A / cm 2 , which is four orders of magnitude lower than the current density of the uncoated magnesium sheet, indicating the superior protective performance of the coated magnesium sheet.

[0111] Although the present invention has been disclosed as above, the present invention 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 invention. Therefore, the protection scope of the present invention should be based on the scope defined by the claims.

Claims

1. A composite coating comprising Coating I and Coating II deposited on a substrate, said coating I being a plasma polymerized coating formed by a plasma containing monomer α and monomer β; the coating II is a plasma polymerized coating formed on the coating I by contacting the coating I with a plasma comprising monomer γ and monomer δ; The structure of the monomer α is shown in formula (1-1): [Formula 1] (Here, R １ is CH or C ３ ~C ８ R ２ , R ３ and R ４ Each independently represents a bond or C １ ~C ６ and R ２ and R ３ When both are bonds, they are not bonded to the same carbon atom, A is a linking site, and B contains a carbon-carbon unsaturated bond or an epoxy structure. The structure of the monomer β is shown in formula (2-1): [Case 2] (Here, S １ contains one or more -O-C(O)- or -C(O)-O-, R ５ , R ６ , R ７ , R ８ , R ９ and R １０ are each independently a hydrogen atom, a halogen atom, or C １ ~C １０ or C １ ~C １０ is selected from the halogen atom-substituted alkyl groups. The structure of the monomer γ is shown in formula (3-1): [C3] (wherein Ar is a structure having an aromatic ring, T １ is —O—C(O)— or —C(O)—O—, and X １ is a linking site, and Y １ is a linking site, R １１ , R １２ and R １３ are each independently a hydrogen atom, a halogen atom, or C １ ~C １０ or C １ ~C １０ is selected from the halogen atom-substituted alkyl groups. A composite coating, characterized in that the structure of the monomer δ is represented by formula (4-1). [C4] (Here, S ２ contains one or more -O-C(O)- or -C(O)-O-, R １４ , R １５ , R １６ , R １７ , R １８ and R １９ are each independently a hydrogen atom, a halogen atom, or C １ ~C １０ or C １ ~C １０ is selected from the halogen atom-substituted alkyl groups.

2. 2. The composite coating of claim 1, wherein A is --O--C(O)-- or --C(O)--O--.

3. The composite coating according to claim 2, wherein the structure of the monomer α is represented by formula (1-2). [C5] (Here, R ２０ , R ２１ and R ２２ are each independently a hydrogen atom, a halogen atom, or C １ ~C １０ or C １ ~C １０ is selected from the halogen atom-substituted alkyl groups.

4. The R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ , R １８ and R １９ 2. The composite coating of claim 1, wherein each is independently selected from a hydrogen atom or a methyl group.

5. The R ２０ , R ２１ and R ２２ 4. The composite coating of claim 3, wherein each is independently selected from a hydrogen atom or a methyl group.

6. 2. The composite coating of claim 1, wherein the monomer α is selected from one or more of glycidyl methacrylate, tetrahydrofurfuryl acrylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, 1,2-epoxy-4-vinylcyclohexane, bis(2,3-epoxycyclopentyl)ether, 2,3-epoxycyclopentyl cyclopentyl ether, vinylcyclohexene dioxide, diisoprene dioxide, or bis((3,4-epoxycyclohexyl)methyl)adipate.

7. The S １ and / or S ２ The composite coating of claim 1, characterized in that it contains two -O-C(O)- or -C(O)-O- groups.

8. The S １ The composite coating of claim 7, characterized in that the structure is shown in formula (2-2). [C6] (Here, R ２３ is C ２ ~C １０ or an alkylene group of C ２ ~C １０ and y is an integer of 0 to 10.

9. 2. The composite coating of claim 1, wherein the monomer β 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, neopentyl glycol dimethacrylate, methacrylic anhydride, diprop-2-enyl 2-methylene succinate, diprop-2-enyl 2-benzylidene malonate, or diethyl diallyl malonate.

10. The X １ The composite coating of claim 1, characterized in that the structure is shown in formula (3-2). [C7] (Here, X １１ is a bond, —O— or —C(O)—, and X １２ is a bond, C １ ~C １０ or an alkylene group of C １ ~C １０ is a halogen atom-substituted alkylene group represented by the formula: The Y １ is a bond, C １ ~C １０ or an alkylene group of C １ ~C １０ is a halogen atom-substituted alkylene group.

11. 2. The composite coating of claim 1, wherein Ar is a benzene ring structure or a substituted benzene ring structure.

12. The composite coating of claim 11, wherein the monomer γ structure is represented by formula (3-3): [C8] (Here, T ２ is —O—C(O)— or —C(O)—O—, and X ２ is a linking site, and Y ２ is the linking site, R ２４ , R ２５ and R ２６ are each independently a hydrogen atom, a halogen atom, or C １ ~C １０ or C １ ~C １０ is selected from the halogen atom-substituted alkyl groups.

13. The X ２ The composite coating according to claim 12, characterized in that the structure is shown in formula (3-4): [C9] (Here, X ２１ is a bond, —O— or —C(O)—, and X ２２ is a bond, C １ ~C １０ or an alkylene group of C １ ~C １０ is a halogen atom-substituted alkylene group represented by the formula: The Y ２ is a bond, C １ ~C １０ Alkylene group D or C １ ~C １０ is a halogen atom-substituted alkylene group.

14. The R ２４ , R ２５ and R ２６ 13. The composite coating of claim 12, wherein each is independently selected from a hydrogen atom or a methyl group.

15. 2. The composite coating of claim 1, wherein the monomer γ is selected from at least one of 2-phenoxyethyl acrylate, phenyl acrylate, diallyl terephthalate, or phenyl methacrylate.

16. The S ２ The composite coating of claim 7, characterized in that the structure is shown in formula (4-2). [C10] (Here, R ２７ is C ２ ~C １０ or an alkylene group of C ２ ~C １０ and z is an integer of 0 to 10.

17. 2. The composite coating of claim 1, 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, neopentyl glycol dimethacrylate, methacrylic anhydride, diprop-2-enyl 2-methylene succinate, diprop-2-enyl 2-benzylidene malonate, or diethyl diallyl malonate.

18. the composite coating further comprises a coating III, which is a plasma polymerized coating formed on the coating II by contacting the coating II with a plasma comprising a monomer ε; The composite coating according to claim 1, wherein the structure of the monomer ε is shown in formula (5-1). [C11] where Z is a linking moiety and R ２８ , R ２９ and R ３０ are each independently a hydrogen atom, a halogen atom, or C １~C １０ or a hydrocarbon group of C １ ~C １０ wherein x is an integer of 1 to 20.

19. Z is a bond, C １ ~C ４ or a C having a substituent １ ~C ４ 20. The composite coating of claim 18, wherein x is an alkylene group of the formula:

20. The R ２８ , R ２９ and R ３０ 20. The composite coating of claim 18, wherein each is independently selected from a hydrogen atom or a methyl group.

21. 19. The composite coating of claim 18, wherein the monomer ε is selected from one or more of 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl methacrylate, 2-(perfluorodecyl)ethyl methacrylate, 2-(perfluorohexyl)ethyl methacrylate, 2-(perfluorododecyl)ethyl acrylate, 2-(perfluorooctyl)ethyl acrylate, 1H,1H,2H,2H-perfluorooctyl acrylate, 2-(perfluorobutyl)ethyl acrylate, (2H-perfluoropropyl)-2-acrylate or (perfluorocyclohexyl)methyl acrylate.

22. The composite coating according to claim 1, characterized in that the thickness of the composite coating is 50-300 nm.

23. 2. The composite coating of claim 1, wherein the molar ratio of monomer α to monomer β is between 1:5 and 5:

1.

24. 2. The composite coating according to claim 1, wherein the molar ratio of monomer γ to monomer δ is between 3:10 and 10:

3.

25. 10. The composite coating of claim 1, wherein the substrate is a metal, plastic, fabric, glass, electrical component, optical device, or electrical part.

26. A substrate is provided and placed in a plasma reaction chamber, which is evacuated to 20-200 mTorr and filled with an inert gas such as He, Ar, or O. ２ or introducing some mixture of gases; Introducing a mixed monomer vapor of monomer α and monomer β into the reaction chamber and initiating a plasma discharge to form a plasma polymerized coating I; and introducing a mixed monomer vapor of monomer γ and monomer δ into the reaction chamber and initiating a plasma discharge to form a plasma polymerized coating II on the coating I; A method for producing a composite coating according to any one of claims 1 to 25, comprising:

27. 27. A method for producing a composite coating according to claim 26, characterized in that monomer ε vapor is introduced into the reaction chamber and plasma discharge is initiated to form a plasma polymerized coating III on the coating II.

28. 27. The method of claim 26, wherein the plasma is a pulsed plasma.

29. 29. The method for producing a composite coating according to claim 28, characterized in that the pulsed plasma is generated by applying a pulse voltage discharge, the pulse power being 50W-500W, the pulse frequency being 25Hz-85kHz, the pulse duty ratio being 5%-85%, and the plasma discharge time being 100s-36000s.

30. A device, characterized in that at least a part of the surface of the device comprises a composite coating according to any one of claims 1 to 25.

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