TWI828073B - Composite coating, preparation method and device - Google Patents

Abstract

A specific embodiment of the present invention provides a composite coating, which uses a coating formed by plasma of fluorine-containing acrylate as the outer layer, and a coating formed by plasma of an unsaturated ester monomer with an aromatic ring and an ester coupling agent. As the inner layer, the composite coating and the substrate formed together have excellent protective properties and good transparency.

Description

Composite coating, preparation method and device

The invention belongs to the field of plasma chemistry, and specifically relates to a plasma polymerization composite coating and a preparation method thereof.

As the durability requirements of electronic 3C products increase, waterproof treatment has become the choice of many electronic products. Nano waterproof technology will not change the internal or external structure of electronic products, nor will it increase the weight of the product itself. It can be widely used in various high-tech fields such as solar energy, communication equipment, light-emitting diode (LED) waterproofing, precision integrated circuit (IC) packaging, circuit board integration, automotive electronics and other high-tech fields. This nano-waterproof technology mainly uses nano-level molecular organic coating materials to perfectly encapsulate electronic products in a vacuum and dust-free environment, forming a nano-water-resistant film on the protective components so that water molecules cannot contact and be protected. element.

When using the vacuum coating process, due to differences in coating power, temperature, flow rate and coating gas spray characteristics, even if there is fixture support, it is still easy for the coated product to have uneven thickness and lead to discoloration. The process of Plasma Enhanced Chemical Vapor Deposition (PECVD) uses microwaves or radio frequencies to ionize gases containing film components to form plasma locally. The plasma is very chemically active and can easily react. The desired nano-water-resistant film can be deposited on the substrate. How to use PECVD to develop coatings with excellent protective effects and high transparency has become a hot topic in the market.

The specific embodiment of the present invention is to provide a composite coating, a preparation method and a device that not only have excellent protective properties with the substrate but also have good transparency. The specific scheme is as follows: a composite coating, the composite coating includes deposition Coating I and coating II on the substrate, the coating I is a plasma polymerization coating formed by a plasma containing monomer α and monomer β; the coating II is contacted by the coating I Plasma containing monomer γ, thereby forming a plasma polymerization coating on the coating I; the monomer α has a structure shown in formula (1-1),

Among them, Ar is a structure with an aromatic ring, T ₁ is -OC(O)- or -C(O)-O-, X ₁ is the connecting part, Y ₁ is the connecting part, R ₁ , R ₂ and R ₃ are respectively Independently selected from a hydrogen atom, a halogen atom, a C ₁ -C ₁₀ alkyl group or a C ₁ -C ₁₀ halogen atom substituted alkyl group; the monomer β has the structure shown in formula (2-1),

Among them, S contains more than one -OC(O)- or -C(O)-O-, and R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are independently selected from hydrogen atoms, Halogen atom, C ₁ -C ₁₀ alkyl group or C ₁ -C ₁₀ halogen atom substituted alkyl group; the monomer γ has the structure shown in formula (3-1),

Among them, Z is the connecting part, R ₁₀ , R ₁₁ and R ₁₂ are each independently selected from a hydrogen atom, a halogen atom, a C ₁ -C ₁₀ hydrocarbon group or a C ₁ -C ₁₀ halogen atom substituted hydrocarbon group, and x is 1- An integer of 20. Optionally, the R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are independently selected from hydrogen atoms or methyl.

Optionally, the X ₁ is a structure shown in the following formula (1-2), *-X ₁₁ -X ₁₂ -* (1-2)

_{wherein , _ _ _ _} Y ₁ is a connecting bond, a C ₁ -C ₁₀ alkylene group, or a C ₁ -C ₁₀ halogen atom-substituted alkylene group.

Optionally, the Ar is a benzene ring structure or a benzene ring structure with a substituent.

Optionally, the monomer α has the structure shown in formula (1-3),

Among them, T ₂ is -OC(O)- or -C(O)-O-, X ₂ is the connecting part, and Y ₂ is the connecting part; R ₁₃ , R ₁₄ and R ₁₅ are independently selected from hydrogen atoms, A halogen atom, a C ₁ -C ₁₀ alkyl group, or a C ₁ -C ₁₀ halogen atom substitutes the alkyl group.

Optionally, the X ₂ is a structure shown in the following formula (1-4), *-X ₂₂ -X ₂₁ -* (1-4)

_{wherein , _ _ _ _} Y ₂ is a connecting bond, a C ₁ -C ₁₀ alkylene group or a C ₁ -C ₁₀ halogen atom-substituted alkylene group.

Optionally, R ₁₃ , R ₁₄ and R ₁₅ are each independently selected from a hydrogen atom or a methyl group.

Optionally, the monomer α is selected from at least one of 2-phenoxyethyl acrylate, phenyl acrylate, diallyl terephthalate or phenyl methacrylate.

Optionally, the S contains two -O-C(O)- or -C(O)-O-, and x is more than 5.

Optionally, the S has the structure shown in formula (2-2),

Wherein, R ₁₆ is a C ₂ -C ₁₀ alkylene group or a C ₂ -C ₁₀ halogen atom substituted alkylene group, and y is an integer from 0 to 10.

Optionally, the monomer β is selected from 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, dimethyl Diethylene glycol acrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, Methacrylic anhydride, dipropylene-2-enyl-2-methylenesuccinate, dipropylene-2-enyl 2-benzylidenemalonate or diethyl diallylmalonate at least one of them.

Optionally, Z is a connecting bond, a C ₁ -C ₄ alkylene group or a C ₁ -C ₄ alkylene group with a substituent.

Optionally, the monomer γ is selected from 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl methacrylate, 2-(perfluorodecyl)ethyl methacrylate, 2-(Perfluorohexyl)ethyl methacrylate, 2-(Perfluorododecanyl)ethyl acrylate, 2-Perfluorooctyl acrylate ethyl ester, 1H,1H,2H,2H-Perfluorooctyl One or more of alcohol acrylate, 2-(perfluorobutyl)ethyl acrylate, (2H-perfluoropropyl)-2-acrylate or (perfluorocyclohexyl) methacrylate.

Optionally, the thickness of coating I is 80-800 nm, and the thickness of coating II is 10-50 nm.

Optionally, the molar ratio of monomer α and monomer β is between 3:10 and 10:3.

Optionally, the substrate is an electronic or electrical component.

Optionally, the base material is a mobile phone, tablet computer, keyboard, e-reader, wearable device, display, earphone, Universal Serial Bus (USB) data cable, USB interface, sound-transparent mesh, earphone Cover or headband.

Optionally, the thickness of coating I is 80-130 nm, and the thickness of coating II is 10-50 nm.

A method for preparing any of the above composite coatings, including: providing a substrate, placing the substrate in a plasma reaction chamber, vacuuming to 20-250 mTorr, and passing inert gases He, Ar, and O ₂ or several mixed gases; introduce the mixed monomer vapor of monomer α and monomer β into the reaction chamber, turn on the plasma discharge, and form the plasma polymerization coating I; introduce the monomer γ vapor into the reaction chamber, turn on Plasma discharge forms plasma polymerized coating II on coating I.

Optionally, the plasma is pulsed plasma.

Optionally, the pulsed plasma is generated by applying pulse voltage discharge, wherein the pulse power is 10W-100W, the pulse frequency is 15Hz-60kHz, the pulse duty cycle is 1%~85%, and the plasma discharge time is 100s-36000s. .

A device, at least part of the surface of the device has any one of the above-mentioned composite coatings.

A composite coating, the composite coating comprising a coating I deposited on a substrate, the coating I being a plasma polymerization coating formed by a plasma containing monomer α and monomer β; the monomer α has the structure shown in formula (1-1),

Among them, Ar is a structure with an aromatic ring, T ₁ is -OC(O)- or -C(O)-O-, X ₁ is the connecting part, Y ₁ is the connecting part, R ₁ , R ₂ and R ₃ are respectively Independently selected from a hydrogen atom, a halogen atom, a C ₁ -C ₁₀ alkyl group or a C ₁ -C ₁₀ halogen atom substituted alkyl group; the X ₁ is a structure represented by the following formula (1-2), * -X ₁₁ -X ₁₂ -* (1-2)

_{Wherein , _ _ _ _ _} C ₁ -C ₁₀ alkylene group or C ₁ -C ₁₀ halogen atom substituted alkylene group; the monomer β has the structure shown in formula (2-1),

Among them, S contains more than one -OC(O)- or -C(O)-O-, and R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are independently selected from hydrogen atoms, A halogen atom, a C ₁ -C ₁₀ alkyl group, or a C ₁ -C ₁₀ halogen atom substitutes the alkyl group.

Optionally, the Ar is a benzene ring structure or a benzene ring structure with a substituent.

Optionally, the R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are each independently selected from a hydrogen atom or a methyl group.

Optionally, the monomer α is 2-phenoxyethyl acrylate.

Optionally, the S contains two -O-C(O)- or -C(O)-O-, and x is more than 5.

Optionally, the S has the structure shown in formula (2-2),

Wherein, R ₁₆ is a C ₂ -C ₁₀ alkylene group or a C ₂ -C ₁₀ halogen atom substituted alkylene group, and y is an integer from 0 to 10.

Optionally, the monomer β is selected from 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, dimethyl Diethylene glycol acrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, Methacrylic anhydride, dipropylene-2-enyl-2-methylenesuccinate, dipropylene-2-enyl 2-benzylidenemalonate or diethyl diallylmalonate at least one of them.

Optionally, the molar ratio of monomer α and monomer β is between 3:10 and 10:3.

The composite coating of the specific embodiment of the present invention uses a coating formed by plasma of fluorine-containing acrylate as the outer layer, and a coating formed by plasma of unsaturated ester monomers with aromatic rings and ester coupling agents as the inner layer. layer, the composite coating and the substrate formed together not only have excellent protective properties, but also have good transparency.

A composite coating according to a specific embodiment of the present invention. The composite coating includes a coating I and a coating II deposited on a substrate. The coating I is formed by a plasma containing monomer α and monomer β. The coating II is a plasma polymerization coating formed on the coating I by contacting the coating I with a plasma containing monomer γ; the monomer α has the formula (1-1 ), the structure shown in

Among them, Ar is a structure with an aromatic ring, T ₁ is -OC(O)- or -C(O)-O-, X ₁ is the connecting part, Y ₁ is the connecting part, R ₁ , R ₂ and R ₃ are respectively Independently selected from a hydrogen atom, a halogen atom, a C ₁ -C ₁₀ alkyl group or a C ₁ -C ₁₀ halogen atom substituted alkyl group; the monomer β has the structure shown in formula (2-1),

Among them, S contains more than one -OC(O)- or -C(O)-O-, and R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are independently selected from hydrogen atoms, Halogen atom, C ₁ -C ₁₀ alkyl group or C ₁ -C ₁₀ halogen atom substituted alkyl group; the monomer γ has the structure shown in formula (3-1),

Among them, Z is the connecting part, R ₁₀ , R ₁₁ and R ₁₂ are each independently selected from a hydrogen atom, a halogen atom, a C ₁ -C ₁₀ hydrocarbon group or a C ₁ -C ₁₀ halogen atom substituted hydrocarbon group, and x is 1- An integer of 20.

The inventor of the present invention found through research that the coating formed by fluorine-containing acrylate plasma has Good hydrophobicity and extremely weak hygroscopicity, which can effectively prevent solutions and moisture from intruding into the interior. It also has the advantages of high transparency and UV resistance. It is an unsaturated ester monomer with an aromatic ring and an ester coupling agent. The coating formed by the plasma has a high molar refractive index and a relatively small molecular volume, and can enhance the bonding force between the coating formed by the fluorine-containing acrylate plasma and the substrate. By using the fluorine-containing acrylate The coating formed by plasma is used as the outer layer, and the coating formed by plasma of ester monomers with aromatic rings and ester coupling agents is used as the inner layer. The composite coating formed together not only has excellent protective properties, but also Has good transparency.

Composite coating according to specific embodiments of the present invention. In some specific implementations, the Ar is a benzene ring or a heteroaromatic ring with a substituent on the aromatic ring. In other specific implementations, the Ar is an aromatic ring. An unsubstituted benzene ring or heteroaromatic ring.

In the composite coating according to the specific embodiment of the present invention, X ₁ and Y ₁ are connecting parts, X ₁ is used to connect the structure Ar with an aromatic ring and the ester bond T ₁ , and Y ₁ is used to connect the ester bond T ₁ and the saturated Carbon-carbon double bond. In some specific embodiments, X ₁ is a structure represented by the following formula (1-2), *-X ₁₁ -X ₁₂ -* (1-2)

_{wherein , _ _ _ _} Y ₁ is a connecting bond, a C ₁ -C ₁₀ alkylene group, or a C ₁ -C ₁₀ halogen atom-substituted alkylene group. The alkylene group includes linear alkylene groups, such as methylene, ethylene, propylene or butylene, or branched alkylene groups, such as isopropylene or isobutylene, etc. .

The composite coating of specific embodiments of the present invention, in some specific embodiments, the R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently selected from a hydrogen atom or a methyl group.

The composite coating according to specific embodiments of the present invention, in some specific embodiments, the monomer α has the structure shown in formula (1-3),

Among them, T ₂ is -OC(O)- or -C(O)-O-, X ₂ is the connecting part, used to connect the benzene ring and the ester bond T ₂ , Y ₂ is the connecting part, used to connect the ester bond T ₂ and carbon-carbon double bonds; R ₁₃ , R ₁₄ and R ₁₅ are each independently selected from a hydrogen atom, a halogen atom, a C ₁ -C ₁₀ alkyl group or a C ₁ -C ₁₀ halogen atom substituted alkyl group. The alkyl group includes a straight chain alkyl group, such as methyl, ethyl, propyl or butyl, or a branched alkyl group, such as isopropyl or isobutyl.

In the composite coating according to the specific embodiments of the present invention, in some specific embodiments, in the structure shown in formula (1-3), the two substituents on the benzene ring are para-substituted. In other embodiments, they can also be It is collar substitution or metaposition substitution.

In the composite coating according to specific embodiments of the present invention, in some specific embodiments, X ₂ is a structure represented by the following formula (1-4), *-X ₂₂ -X ₂₁ -* (1-4)

_{wherein , _ _ _ _} Y ₂ is a connecting bond, a C ₁ -C ₁₀ alkylene group or a C ₁ -C ₁₀ halogen atom-substituted alkylene group. The alkylene group includes linear alkylene groups, such as methylene, ethylene, propylene or butylene, or branched alkylene groups, such as isopropylene or isobutylene, etc. .

In the composite coating according to specific embodiments of the present invention, in some specific embodiments, R ₁₃ , R ₁₄ and R ₁₅ are each independently selected from a hydrogen atom or a methyl group.

For the composite coating of the specific embodiment of the present invention, as a specific non-limiting example, the monomer α is selected from 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 No.: 2177-70-0) at least one.

Composite coating according to specific embodiments of the present invention, in some specific implementations, the S contains two -O-C(O)- or -C(O)-O-, that is, the S contains two -O-C(O )-, two -C(O)-O- or -O-C(O)- or -C(O)-O-, one each; the x is above 5, for example, it can be 5, 6, 7, 8, 9, 10, 11 or 12 etc.

The composite coating of the specific embodiment of the present invention, in some specific embodiments, the S has the structure shown in formula (2-2),

Wherein, R ₁₆ is a C ₂ -C ₁₀ alkylene group or a C ₂ -C ₁₀ halogen atom substituted alkylene group. The alkylene group includes a straight chain alkylene group, such as methylene, ethylene, Propylene or butylene, etc., or branched alkylene, such as isopropylene or isobutylene, etc., y is an integer from 0 to 10. Specifically, it is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

For the composite coating according to the specific embodiment of the present invention, as a specific non-limiting example, the monomer β is selected from 1,4-butanediol dimethacrylate (CAS No.: 2082-81-7), dimethacrylate 1,6-hexanediol methacrylate (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), tetraethylene glycol dimethacrylate (CAS number: 109-17-1) , 1,3-butanediol dimethacrylate (CAS No.: 1189-08-8), neopentyl glycol dimethacrylate (CAS No.: 1985-51-9), methacrylic anhydride (CAS No.: 760-93-0), dipropylene-2-enyl-2-methylenesuccinate, dipropylene-2-enyl 2-benzylidene malonate (CAS No.: 52505-39 -2) or at least one of diethyl diallylmalonate (CAS No.: 3195-24-2).

In the composite coating according to the specific embodiment of the present invention, the Z is a connecting part used to connect the ester bond perfluorocarbon alkyl group. In some specific embodiments, the Z is a connecting bond, a C ₁ -C ₄ alkylene group or a C ₁ -C ₄ alkylene group having a substituent. The alkylene group includes linear alkylene groups, such as methylene, ethylene, propylene or butylene, or branched alkylene groups, such as isopropylene or isobutylene, etc. , the substituent includes, for example, a halogen atom, a hydroxyl group, a carboxyl group or an ester group, etc.

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

For the composite coating of the specific embodiment of the present invention, as a specific non-limiting example, the monomer γ is selected from 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl methacrylate (CAS No.: 16083-81-1), 2-(Perfluorodecyl)ethyl methacrylate (CAS No.: 2144-54-9), 2-(Perfluorohexyl)ethyl methacrylate (CAS No. : 2144-53-8), 2-(Perfluorododecanyl)ethyl acrylate (CAS No.: 27905-45-9), 2-Perfluorooctyl ethyl acrylate (CAS No.: 27905-45- 9), 1H, 1H, 2H, 2H-perfluorooctanol acrylate (CAS number: 17527-29-6), 2-(perfluorobutyl) ethyl acrylate (CAS number: 52591-27-2) , one or more of (2H-perfluoropropyl)-2-acrylate (CAS number: 59158-81-5) or (perfluorocyclohexyl) methacrylate (CAS number: 40677-94-9) species.

The composite coating of the specific embodiment of the present invention, in some specific embodiments, the coating I is a plasma polymerization coating formed by the plasma of monomer α and monomer β; the coating II is formed by the plasma of monomer α and monomer β. Layer I is exposed to the plasma of monomer γ, thereby forming a plasma polymerized coating on coating I. In other specific embodiments, without affecting the overall coating properties of coating I and coating II, coating I can be made of monomer α and monomer β plus plasma of appropriate other monomers. The plasma polymerization coating formed by the monomer; the coating II can be contacted by the coating I with a mixed monomer plasma of monomer γ and appropriate other monomers, thereby forming a plasma polymerization coating on the coating I layer.

The composite coating according to specific embodiments of the present invention. In some specific implementations, the thickness of coating I is 80-800 nm, and the thickness of coating II is 10-50 nm. This coating thickness is beneficial to maintaining the coating transparency and protective properties.

In the composite coating according to specific embodiments of the present invention, in some specific implementations, the molar ratio of monomer α and monomer β is between 3:10 and 10:3. For example, it can be 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.; in other specific implementations, in full Taking into account both protective performance and transparency, other proportions can also be adjusted according to the specific monomer conditions.

In the composite coating according to specific embodiments of the present invention, in some specific embodiments, the substrate is various plastics, fabrics, glass, electrical components or optical instruments, etc. Specifically, the electrical component may be a printed circuit board (PCB), electronic product or electronic assembly semi-finished product, etc.

In some specific embodiments, the substrate is an electronic or electrical component. As a specific non-limiting example, when the substrate is an electronic product, it can be a mobile phone, a tablet computer, a keyboard, an e-reader, or an electronic product. Wearable devices, monitors, headphones, USB data cables, USB interfaces, sound-transparent mesh, earmuffs or headbands, etc. The substrate can also be any suitable electrical component of an electrical component. Specifically, the electrical component can be a resistor, a capacitor, a transistor, a diode, an amplifier, a relay, a transformer, a battery, a fuse, an accumulator. Body circuits, switches, LEDs, LED displays, piezoelectric components, optoelectronic components or antennas or oscillators, etc. For these substrates, generally in order to ensure their transparency, the thickness of the coating I is 80-130 nm, and the thickness of the coating II is 10-50 nm.

Specific embodiments of the present invention also provide a method for preparing any of the above composite coatings, including: providing a substrate, placing the substrate in a plasma reaction chamber, vacuuming to 20-250 mTorr, and passing in Inert gas He, Ar, O ₂ or several mixed gases; introduce monomer α and monomer β mixed monomer vapor into the reaction chamber, start plasma discharge to form plasma polymerization coating I; add monomer γ Steam is introduced into the reaction chamber, plasma discharge is started, and a plasma polymerized coating II is formed on the coating I.

In the composite coating preparation method according to the specific embodiment of the present invention, the monomer α, monomer β, monomer γ, coating I, coating II, substrate, etc. are described as above.

The composite coating preparation method of the specific embodiment of the present invention is different from other plasma coatings in that it is preferable not to perform continuous wave plasma treatment on the surface of the substrate before plasma coating, which is beneficial to maintaining the transparency of the coating product.

In the composite coating preparation method according to specific embodiments of the present invention, in some specific implementations, the plasma is pulse plasma, and the monomer flow rate is 50-500ul/min, for example, it can be 100ul/min, 200ul/min. min, 300ul/min or 400ul/min, etc.; the temperature in the cavity is controlled at 20℃-80℃, for example, it can be 20℃, 30℃, 40℃, 50℃, 60℃, 70℃ or 80℃, etc. ;The vaporization temperature of the monomer is 50℃-120℃, for example, it can be 50℃, 60℃, 70℃, 80℃, 90℃, 100℃, 110℃ or 120℃, etc., and it occurs under vacuum conditions Gasification, the pulse plasma is generated by applying pulse voltage discharge, wherein the pulse power is 10W-100W, specifically, it can be 10W, 20W, 30W, 40w, 50w, 60w, 70w, 80w, 90w or 100w, etc.; The pulse frequency is 15Hz-60kHz, for example, it can be 15Hz, 20Hz, 25Hz, 30Hz, 35Hz, 40Hz, 45Hz, 50Hz, 55Hz or 60Hz, etc.; the pulse duty cycle is 1%~85%, for example it can be 1% , 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or 85 % and so on; the plasma discharge time is 100s-36000s, specifically, it can be 100s, 500s, 1000s, 2000s, 3000s, 4000s, 5000s, 6000s, 7000s, 8000s, 9000s, 10000s, 15000s, 20000s, 25000s, 30000s , 36000s, etc. wait.

In the composite coating preparation method of the specific embodiment of the present invention, in some specific implementations, the plasma discharge method can be various existing discharge methods, specifically, for example, electrodeless discharge (such as radio frequency inductive coupling discharge, microwave discharge), single electrode Discharge (such as corona discharge, plasma jet formed by unipolar discharge), two-electrode discharge (such as dielectric barrier discharge, exposed electrode radio frequency glow discharge) and multi-electrode discharge (such as discharge using a floating electrode as the third electrode) .

Specific embodiments of the present invention also provide a device, at least part of the surface of the device has any one of the above-mentioned composite coatings. In some specific embodiments, part or all of the surface of the device is only coated with the above-mentioned composite coating. protective coating.

The present invention will be further described below through specific examples.

Example

Test method description

Salt spray resistance test: conducted according to GB/T 2423.18-2000 Environmental Test Method for Electrical and Electronic Products detection.

Colorimetric test: Tested according to GB/T3979--2008 standard.

Water drop angle test: Tested according to GB/T 30447-2013 standard.

Coating thickness test: Use American Filmetrics F20-UV-film thickness measuring instrument for testing.

Example 1

(1) Place the substrate mic-usb in a 500L plasma vacuum reaction chamber, and continuously evacuate the reaction chamber to achieve a vacuum degree of 120 mTorr. The internal temperature of the chamber is 45°C, and helium is introduced with a flow rate of 160 sccm. ; (2) Pass in triethylene glycol dimethacrylate and 2-phenoxyethyl acrylate (mass ratio 1:1) mixed monomers, the mixed monomer flow rate is 200ul/min, and the monomer vaporization temperature is 110℃, turn on the radio frequency plasma discharge, the radio frequency energy output mode is pulse, the discharge time is 2800s, the discharge power is 10w, the pulse frequency is 15Hz, the pulse duty cycle is 25%, to form coating I; (3) Then pass into the single Monomer 2-(perfluorohexyl)ethyl methacrylate, monomer flow rate is 200ul/min, monomer vaporization temperature is 110℃, discharge time is 900s, discharge power is 50w, pulse frequency is 25Hz, pulse duty cycle is 35% , to form coating II; (4) After the coating preparation is completed, introduce air to return the reaction chamber to normal pressure, open the chamber, take out the mic-usb to measure the coating thickness, chromaticity value, water droplet angle and salt spray Test, the test results are listed in Table 1 below.

Example 2

(1) Place the substrate Type-C in a 500L plasma vacuum reaction chamber. Continuously evacuate the reaction chamber to achieve a vacuum degree of 80 mTorr. The internal temperature of the chamber is 35°C. Helium gas is introduced with a flow rate of 100 sccm. ; (2) Pass in the mixed monomer of 1,6-hexanediol dimethacrylate and phenyl acrylate (mass ratio 3:2), the flow rate of the mixed monomer is 250ul/min, and the monomer vaporization temperature is 180°C , turn on the radio frequency plasma discharge, the radio frequency energy output mode is pulse, the discharge time is 3600s, the discharge power is 25w, the pulse frequency is 45Hz, the pulse duty cycle is 45%, and the coating I is formed; (3) Then the monomer 2- (Perfluorodecyl)ethyl acrylate, monomer flow rate is 150ul/min, the monomer vaporization temperature is 120℃, the discharge time is 1300s, the discharge power is 60w, the pulse frequency is 35Hz, and the pulse duty cycle is 20% to form coating II; (4) After the coating preparation is completed, air is introduced, Return the reaction chamber to normal pressure, open the chamber, and take out Type-C to conduct coating thickness, chromaticity value, water drop angle, and salt spray tests. The test results are listed in Table 1 below.

Example 3

(1) Place the base material earphone semi-finished product in a 500L plasma vacuum reaction chamber, continuously evacuate the reaction chamber to achieve a vacuum degree of 80 mTorr, the internal temperature of the chamber is 35°C, and introduce helium gas with a flow rate of 40 sccm; (2) Pour in the mixed monomer of triethylene glycol dimethacrylate and phenyl methacrylate (mass ratio 2:3), the flow rate of the mixed monomer is 500ul/min, and the monomer vaporization temperature is 180°C. Turn on Radio frequency plasma discharge, the energy output mode of radio frequency is pulse, the discharge time is 7200s, the discharge power is 10w, the pulse frequency is 60Hz, and the pulse duty cycle is 45% to form the coating I; (3) and then pass into the monomer 2-(full Fluorobutyl)ethyl acrylate, the monomer flow rate is 150ul/min, the monomer vaporization temperature is 110°C, the discharge time is 1800s, the discharge power is 80w, the pulse frequency is 50Hz, and the pulse duty cycle is 25% to form coating II; (4) After the coating preparation is completed, introduce air to return the reaction chamber to normal pressure, open the chamber, and take out the semi-finished earphones for coating thickness, chromaticity value, water droplet angle and salt spray testing. The test results are listed below in FIG. 1.

Example 4

(1) Place the substrate Type-C in a 500L plasma vacuum reaction chamber. Continuously evacuate the reaction chamber to achieve a vacuum degree of 120 mTorr. The internal temperature of the chamber is 35°C. Helium is introduced and the flow rate is 60 sccm. ; (2) Pass in the mixed monomer of tetraethylene glycol dimethacrylate and diallyl terephthalate (mass ratio 3:2), the flow rate of the mixed monomer is 300ul/min, and the monomer vaporization temperature is 160℃, turn on the radio frequency plasma discharge, the radio frequency energy output mode is pulse, the discharge time is 7200s, the discharge power is 30w, the pulse frequency is 15Hz, and the pulse duty cycle is 30%, forming coating I; (3) Then feed the monomer (perfluorocyclohexyl) methacrylate, the monomer flow is 250ul/min, the monomer vaporization temperature is 110°C, the discharge time is 1800s, the discharge power is 60w, the pulse frequency is 50Hz, and the pulse The duty cycle is 45% to form coating II; (4) After the coating preparation is completed, air is introduced to return the reaction chamber to normal pressure, open the chamber, and take out Type-C to measure the coating thickness and chromaticity value. Water drop angle and salt spray test, the test results are listed in Table 1 below.

Example 5

(1) Place the complete base material earphone in a 500L plasma vacuum reaction chamber, and continuously evacuate the reaction chamber to achieve a vacuum degree of 120 mTorr. The internal temperature of the chamber is 35°C. Helium is introduced with a flow rate of 300 sccm. ; (2) Pass in the mixed monomer of 1,4-butanediol dimethacrylate and phenyl acrylate (mass ratio 3:2), the flow rate of the mixed monomer is 200ul/min, and the monomer vaporization temperature is 110°C , turn on the radio frequency plasma discharge, the radio frequency energy output mode is pulse, the discharge time is 7200s, the discharge power is 100w, the pulse frequency is 35Hz, the pulse duty cycle is 25%, and the coating I is formed; (3) Then the monomer 2- (Perfluorobutyl)ethyl acrylate, the monomer flow rate is 200ul/min, the monomer vaporization temperature is 110°C, the discharge time is 1800s, the discharge power is 50w, the pulse frequency is 25Hz, and the pulse duty cycle is 40% to form a coating II; (4) After the coating preparation is completed, air is introduced to return the reaction chamber to normal pressure, open the chamber, and take out the complete headset to conduct coating thickness, chromaticity value, water drop angle and salt spray tests. Test results Listed in Table 1 below.

Example 6

(1) Place the substrate glass piece in a 500L plasma vacuum reaction chamber, continuously evacuate the reaction chamber to achieve a vacuum degree of 80 mTorr, the internal temperature of the chamber is 45°C, and introduce helium gas with a flow rate of 160 sccm; (2) Pass in the mixed monomer of 1,6-hexanediol dimethacrylate and phenyl acrylate (mass ratio 2:3), the flow rate of the mixed monomer is 300ul/min, and the monomer vaporization temperature is 180°C. Turn on the radio frequency plasma discharge, the radio frequency energy output mode is pulse, the discharge time is 7200s, the discharge power is 37w, and the pulse frequency is 20Hz. The pulse duty cycle is 15% to form coating I; (3) Then the monomer 2-(perfluorodecyl)ethyl acrylate is introduced, the monomer flow rate is 200ul/min, and the monomer vaporization temperature is 130℃, discharge time 2600s, discharge power 45w, pulse frequency 30Hz, pulse duty cycle 25% to form coating II; (4) After the coating preparation is completed, air is introduced to return the reaction chamber to normal pressure and open Chamber, take out the glass piece and conduct coating thickness, chromaticity value, water drop angle and salt spray tests. The test results are listed in Table 1 below.

Example 7

(1) Place the black ABS plate as the base material in the 500L plasma vacuum reaction chamber, and continuously evacuate the reaction chamber to achieve a vacuum degree of 100 mTorr. The internal temperature of the chamber is 35°C. Helium gas is introduced with a flow rate of 180 sccm. ; (2) Pass in the mixed monomer of 1,6-hexanediol dimethacrylate and phenyl acrylate (mass ratio 2:3), the flow rate of the mixed monomer is 280ul/min, and the monomer vaporization temperature is 130°C , turn on the radio frequency plasma discharge, the radio frequency energy output mode is pulse, the discharge time is 2000s, the discharge power is 32w, the pulse frequency is 40Hz, the pulse duty cycle is 10%, and the coating I is formed; (3) Then pass into the monomer 2- (Perfluorodecyl) ethyl acrylate, the monomer flow rate is 150ul/min, the monomer vaporization temperature is 160°C, the time is 1200s, the discharge power is 25w, the pulse frequency is 50Hz, and the pulse duty cycle is 25%, forming a coating Layer II; (4) After the coating preparation is completed, air is introduced to return the reaction chamber to normal pressure, open the chamber, and take out the black ABS plate coating thickness, chromaticity value, water drop angle and salt spray test, test results Listed in Table 1 below.

Comparative example 1

(1) Place the substrate mic-usb in a 500L plasma vacuum reaction chamber, and continuously evacuate the reaction chamber to achieve a vacuum degree of 120 mTorr. The internal temperature of the chamber is 45°C. Helium gas is introduced with a flow rate of 160 sccm. ; (2) Pass in the mixed monomer of triethylene glycol dimethacrylate and styrene (mass ratio 1:1), the flow rate of the mixed monomer is 200ul/min, the monomer vaporization temperature is 110°C, and the radio frequency plasma is turned on Body discharge, RF energy output mode is pulse, discharge time is 2800s, discharge power is 10w, pulse frequency is 15Hz, The pulse duty cycle is 25% to form coating I; (3) Then the monomer 2-(perfluorohexyl)ethyl methacrylate is introduced, the monomer flow is 200ul/min, and the monomer vaporization temperature is 110 ℃, discharge time 900s, discharge power 50w, pulse frequency 25Hz, pulse duty cycle 35%, to form coating II; (4) After the coating preparation is completed, introduce air to return the reaction chamber to normal pressure, and open the chamber body, take out the mic-usb and conduct coating thickness, chromaticity value, water drop angle and salt spray tests. The test results are listed in Table 1 below.

Comparative example 2

(1) Place the substrate Type-C in a 500L plasma vacuum reaction chamber. Continuously evacuate the reaction chamber to achieve a vacuum degree of 80 mTorr. The internal temperature of the chamber is 35°C. Helium gas is introduced with a flow rate of 100 sccm. ; (2) Pass in the mixed monomer of 1,6-hexanediol dimethacrylate and p-xylene (mass ratio 3:2), the flow rate of the mixed monomer is 250ul/min, and the monomer vaporization temperature is 180°C. Turn on the radio frequency plasma discharge, the radio frequency energy output mode is pulse, the discharge time is 3600s, the discharge power is 25w, the pulse frequency is 45Hz, and the pulse duty cycle is 45% to form coating I; (3) and then pass into the monomer 2-( Perfluorodecyl)ethyl acrylate, the monomer flow rate is 150ul/min, the monomer vaporization temperature is 120℃, the discharge time is 1300s, the discharge power is 60w, the pulse frequency is 35Hz, and the pulse duty cycle is 20%, forming a coating Layer II; (4) After the coating preparation is completed, air is introduced to return the reaction chamber to normal pressure, open the chamber, and take out Type-C to conduct coating thickness, chromaticity value, water drop angle and salt spray tests. Test The results are listed in Table 1 below.

Comparative example 3

(1) Place the base material earphone semi-finished product in a 500L plasma vacuum reaction chamber, continuously evacuate the reaction chamber to achieve a vacuum degree of 80 mTorr, the internal temperature of the chamber is 35°C, and introduce helium gas with a flow rate of 40 sccm; (2) Introduce the monomer 2-(perfluorobutyl)ethyl acrylate, the monomer flow is 150ul/min, the monomer vaporization temperature is 110°C, turn on the radio frequency plasma discharge, and the radio frequency energy output mode is pulse , discharge The time is 7200s, the discharge power is 80w, the pulse frequency is 50Hz, and the pulse duty cycle is 25% to form coating I; (3) After the coating preparation is completed, air is introduced to return the reaction chamber to normal pressure, open the chamber, and take out The semi-finished products of the earphones were tested for coating thickness, chromaticity value, water drop angle and salt spray. The test results are listed in Table 1 below.

Although the present invention is disclosed as above, the present invention is not limited thereto. Any person 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 subject to the scope defined by the claims.

Claims (22)

A composite coating, characterized in that the composite coating includes a coating I and a coating II deposited on a substrate, and the coating I is formed by a plasma containing monomer α and monomer β. Polymer coating; the coating II is a plasma polymerization coating formed on the coating I by contacting the coating I with a plasma containing monomer γ; the monomer α has the formula (1-1) The structure shown,

Among them, Ar is a structure with an aromatic ring, T ₁ is -OC(O)- or -C(O)-O-, X ₁ is the connecting part, Y ₁ is the connecting part, R ₁ , R ₂ and R ₃ are respectively Independently selected from a hydrogen atom, a halogen atom, a C ₁ -C ₁₀ alkyl group or a C ₁ -C ₁₀ halogen atom substituted alkyl group; the monomer β has the structure shown in formula (2-1),

Among them, S contains more than one -OC(O)- or -C(O)-O-, and R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are independently selected from hydrogen atoms, Halogen atom, C ₁ -C ₁₀ alkyl group or C ₁ -C ₁₀ halogen atom substituted alkyl group; the monomer γ has the structure shown in formula (3-1),

Among them, Z is the connecting part, R ₁₀ , R ₁₁ and R ₁₂ are each independently selected from a hydrogen atom, a halogen atom, a C ₁ -C ₁₀ hydrocarbon group or a C ₁ -C ₁₀ halogen atom substituted hydrocarbon group, and x is 1- An integer of 20. The composite coating according to claim 1, wherein said R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ Each is independently selected from a hydrogen atom or a methyl group. The composite coating according to claim 1, wherein X ₁ is a structure shown in the following formula (1-2), *-X ₁₁ -X ₁₂ -* (1-2) wherein X ₁₁ is a connection bond, -O- or -C(O)-, X ₁₂ is a connecting bond, a C ₁ -C ₁₀ alkylene group or a C ₁ -C ₁₀ halogen atom substituted alkylene group; the Y ₁ is a connecting bond, A C ₁ -C ₁₀ alkylene group or a C ₁ -C ₁₀ halogen atom substitutes the alkylene group. The composite coating according to claim 1, wherein Ar is a benzene ring structure or a benzene ring structure with a substituent. The composite coating according to claim 4, wherein the monomer α has the structure shown in formula (1-3),

Among them, T ₂ is -OC(O)- or -C(O)-O-, X ₂ is the connecting part, and Y ₂ is the connecting part; R ₁₃ , R ₁₄ and R ₁₅ are independently selected from hydrogen atoms, A halogen atom, a C ₁ -C ₁₀ alkyl group, or a C ₁ -C ₁₀ halogen atom substitutes the alkyl group. The composite coating according to claim 5, wherein X ₂ is a structure shown in the following formula (1-4), *-X ₂₂ -X ₂₁ -* (1-4) wherein X ₂₁ is a connection bond, -O- or -C(O)-, X ₂₂ is a connecting bond, a C ₁ -C ₁₀ alkylene group or a C ₁ -C ₁₀ halogen atom substituted alkylene group; the Y ₂ is a connecting bond, A C ₁ -C ₁₀ alkylene group or a C ₁ -C ₁₀ halogen atom substitutes the alkylene group. The composite coating according to claim 5, wherein R ₁₃ , R ₁₄ and R ₁₅ are independently selected from hydrogen atoms or methyl groups. The composite coating according to claim 1, wherein the monomer α is selected from 2-phenoxyethyl acrylate, phenyl acrylate, diallyl terephthalate or phenyl methacrylate. at least one of. The composite coating according to claim 1, wherein the S contains two -O-C(O)- or -C(O)-O-, and x is an integer from 5 to 20. The composite coating according to claim 1, wherein the S has the structure shown in formula (2-2),

Wherein, R ₁₆ is a C ₂ -C ₁₀ alkylene group or a C ₂ -C ₁₀ halogen atom substituted alkylene group, and y is an integer from 0 to 10. The composite coating according to claim 1, wherein the monomer β is selected from 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, dimethyl Ethylene glycol acrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, dimethacrylate Tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, methacrylic anhydride, diprop-2-enyl-2-methylenebutanediol At least one of acid ester, dipropylene-2-enyl 2-benzylidenemalonate or diethyl diallylmalonate. The composite coating according to claim 1, wherein Z is a connecting bond, a C ₁ -C ₄ alkylene group or a C ₁ -C ₄ alkylene group with a substituent. The composite coating according to claim 1, wherein the monomer γ is selected from the group consisting of 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl methacrylate, 2-(perfluorodecyl) ethyl methacrylate, 2-(perfluorohexyl)ethyl methacrylate, 2-(perfluorododecanyl)ethyl acrylate, ethyl 2-perfluorooctyl acrylate, 1H, 1H,2H,2H-Perfluorooctanol acrylate, 2-(perfluorobutyl)ethyl acrylate, (2H-perfluoropropyl)-2-acrylate or (perfluorocyclohexyl) methacrylate one or more of them. The composite coating according to claim 1, wherein the thickness of the coating I is 80-800 nm, and the thickness of the coating II is 10-50 nm. The composite coating according to claim 1, wherein the molar ratio of monomer α and monomer β is between 3:10 and 10:3. The composite coating according to claim 1, wherein the substrate is an electronic or electrical component. The composite coating according to claim 16, wherein the base material is a mobile phone, a tablet computer, a keyboard, an e-reader, a wearable device, a display, an earphone, a USB data cable, a USB interface, a sound-permeable mesh, and an earmuff. Or headband. The composite coating according to claim 17, wherein the thickness of coating I is 80-130 nm, and the thickness of coating II is 10-50 nm. A method for preparing a composite coating according to any one of claims 1-18, characterized in that it includes: providing a substrate, placing the substrate in a plasma reaction chamber, vacuuming to 20-250 mTorr, and passing Enter the inert gas He, Ar, O ₂ or a mixture of several gases; introduce the mixed monomer vapor of monomer α and monomer β into the reaction chamber, start the plasma discharge, and form the plasma polymerization coating I; γ steam is introduced into the reaction chamber, the plasma discharge is started, and a plasma polymerized coating II is formed on the coating I. The method for preparing a composite coating according to claim 19, wherein the plasma is pulsed plasma. The preparation method of the composite coating as described in claim 20, wherein the pulse plasma is generated by applying pulse voltage discharge, wherein the pulse power is 10W-100W, the pulse frequency is 15Hz-60kHz, and the pulse duty cycle is 1% ~85%, plasma discharge time is 100s-36000s. A device with a composite coating, characterized in that at least part of the surface of the device has the composite coating described in any one of claims 1-18.