CN111519168B - Protective coating and preparation method thereof - Google Patents

Protective coating and preparation method thereof Download PDF

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CN111519168B
CN111519168B CN202010520210.9A CN202010520210A CN111519168B CN 111519168 B CN111519168 B CN 111519168B CN 202010520210 A CN202010520210 A CN 202010520210A CN 111519168 B CN111519168 B CN 111519168B
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protective coating
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halogen atom
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CN111519168A (en
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宗坚
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Jiangsu Favored Nanotechnology Co Ltd
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Priority to KR1020237000725A priority patent/KR20230021125A/en
Priority to PCT/CN2021/095010 priority patent/WO2021249156A1/en
Priority to EP21821751.1A priority patent/EP4163417A4/en
Priority to JP2022575845A priority patent/JP7526290B2/en
Priority to US18/008,663 priority patent/US20230242788A1/en
Priority to TW110120898A priority patent/TWI784560B/en
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/22—Esters containing halogen
    • C08F120/24—Esters containing halogen containing perhaloalkyl radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/515—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using pulsed discharges

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Abstract

The invention provides a protective coating, which is a coating formed by plasma polymerization of a monomer A containing a silicon structural unit and a secondary amine structural unit or a primary amine structural unit, a monomer B containing a carboxyl end group structure and a fluorocarbon monomer C on the surface of a base material.

Description

Protective coating and preparation method thereof
Technical Field
The invention belongs to the field of plasma chemistry, and particularly relates to a plasma polymerization protective coating and a preparation method thereof.
Background
The organic polymer coating can effectively protect the surfaces of different materials, for example, electronic and electrical components, metal and the like are easy to corrode and short-circuit under the corrosion of water vapor and liquid, and the polymer protective coating can block the corrosion of the liquid, so that the stability and reliability of electronic products, metal products and the like under moisture or water are improved. At present, a method for preparing a polymer protective coating on the surface of a base material by a vapor deposition method is a mainstream method, and the method has the characteristics of economy, applicability, easy operation and the like, particularly plasma chemical vapor deposition, and utilizes plasma to activate reaction monomer gas and deposit on the surface of the base material. In the plasma preparation of the polymer protective coating, a fluorocarbon resin protective coating is usually prepared on the surface of a substrate by taking a fluorinated compound as a monomer, but the fluorocarbon resin has relatively low strength and is easy to deform under the action of external force, so that the protective coating is easy to lose efficacy. Therefore, how to improve the bonding force and hardness between molecules by designing and regulating the molecular structure so as to further improve the wear resistance of the protective coating is a direction of improvement of the protective coating and a difficult point which needs to be solved urgently.
Disclosure of Invention
In order to solve the problems of poor binding force and poor wear resistance between the protective coating and the base material, the specific embodiment of the invention provides a protective coating and a preparation method thereof, and the specific scheme is as follows:
a protective coating is formed by taking a monomer A, a monomer B and a monomer C as raw materials and depositing the raw materials on the surface of a base material through plasma polymerization;
wherein, the monomer A simultaneously comprises a silicon structural unit of a formula (I) and at least one of an amino structural unit of a formula (II) or a formula (III);
Figure BDA0002531765670000021
monomer B comprises a carboxyl end group structural unit;
the monomer C is selected from one or more of fluorocarbon, fluoroacrylate or fluorosilane.
Optionally, the structure of the monomer A is shown as a formula (IV),
Figure BDA0002531765670000022
wherein X is a connecting bond, an oxygen atom or a carbonyl group, R1Is C1-C10Alkylene or C1-C10A halogen atom-substituted hydrocarbylene group of R2、R3And R4Each independently selected from hydrogen atom, halogen atom, C1-C10A hydrocarbon group of (C)1-C10A halogen atom-substituted hydrocarbon group of (2), C1-C10Hydrocarbyloxy group of (C)1-C10Halogen atom-substituted hydrocarbyloxy group of (1), C1-C10With a hydrocarbon acyloxy group or C1-C10The halogen atom of (a) is substituted with a hydrocarbon acyloxy group.
Optionally, X is a connecting bond, R1Is C1-C10Alkylene of (A), R2、R3And R4Are each independently C1-C10A hydrocarbyloxy group of (1).
Optionally, R1Is ethylene, propylene or butylene, R2、R3And R4Each independently is methoxy, ethoxy or propoxy.
Optionally, the structure of the monomer B is shown as the formula (V),
Figure BDA0002531765670000023
wherein R is5、R6And R7Each independently selected from hydrogen atom, halogen atom, C1-C10Or C is a hydrocarbon group1-C10A halogen atom-substituted hydrocarbon group of (A), Y is a connecting bond, C1-C10Alkylene or C1-C10The halogen atom-substituted alkylene group of (1).
Optionally, the R is5、R6And R7Each independently selected from a hydrogen atom or a methyl group, and Y is a bond.
Optionally, the R is5And R6Is a hydrogen atom, R7Is a hydrogen atom or a methyl group.
Optionally, the fluorocarbon is selected from one or more of a fluoroalkane, a fluoroalkene or a fluoroalkyne.
Optionally, the fluoroacrylate has a structure shown in formula (VI),
Figure BDA0002531765670000031
wherein R is8、R9And R10Each independently selected from hydrogen atom, halogen atom, C1-C10Or C is a hydrocarbon group1-C10X is an integer of 0 to 2, and y is an integer of 1 to 20.
Optionally, R8、R9And R10Each independently selected from a hydrogen atom or a methyl group.
Optionally, the substrate is an electronic or electrical component, or a metal.
Optionally, the molar ratio of monomer A based on amine structural units to monomer B based on carboxyl end group structural units is 10: 0.1-1: 10, respectively.
Optionally, the molar ratio of monomer A based on amine structural units to monomer B based on carboxyl end group structural units is 10: 0.5-1: 5, or more.
Optionally, the molar ratio of the sum of the monomer A and the monomer B to the monomer C is 1: 20-20: 1.
Optionally, the molar ratio of the sum of the monomer A and the monomer B to the monomer C is 1: 5-5: 1.
Optionally, the thickness range of the protective coating is: 1nm-1000 nm.
A method of making a protective coating as described in any of the above, comprising:
providing a substrate, and placing the substrate in a plasma reactor;
and gasifying the monomer A, the monomer B and the monomer C, introducing the gasified monomers into a plasma reactor, discharging the plasma, and polymerizing the plasma on the surface of the base material to form a coating.
Optionally, monomer A and monomer B are mixed before being gasified.
Optionally, the plasma is a pulsed plasma.
Optionally, the pulsed plasma is generated by applying pulsed voltage discharge, wherein the pulse power is 2W-500W, the pulse frequency is 10Hz-50kHz, the pulse duty ratio is 0.1% -80%, and the plasma discharge time is 100s-20000 s.
A device having at least a portion of a surface thereof a protective coating as described above.
The protective coating of the embodiment of the invention is a polymeric coating which is formed by opening and recombining the chemical bonds among the monomer A, the monomer B and the monomer C through plasma, wherein the monomer A contains a silicon structural unit and a secondary amine structural unit or a primary amine structural unit, the monomer B contains a carboxyl end group structure, and the fluorocarbon monomer C, and simultaneously, the secondary amine or the primary amine and the carboxyl end group active functional group can form a three-dimensional network structure firmly combined with a base material, thereby having excellent wear resistance.
Detailed Description
The protective coating of the specific embodiment of the invention is formed by taking a monomer A, a monomer B and a monomer C as raw materials and depositing the raw materials on the surface of a base material through plasma polymerization;
wherein, the monomer A simultaneously comprises a silicon structural unit of a formula (I) and at least one of an amino structural unit of a formula (II) or a formula (III);
Figure BDA0002531765670000041
monomer B comprises a carboxyl end group structural unit; the monomer C is selected from one or more of fluorocarbon, fluoroacrylate or fluorosilane.
The protective coating of the embodiment of the invention is a plasma polymerization coating on the surface of a substrate by using a monomer A containing a silicon structural unit of a formula (I) and a secondary amine structural unit of a formula (II) or a primary amine structural unit of a formula (III), a monomer B containing a carboxyl end group structure and a fluorocarbon monomer C, wherein the monomer A, the monomer B and the monomer C can form a three-dimensional reticular plasma polymerization coating which is firmly combined with the substrate and has excellent wear resistance under the coordination of the silicon-containing structural unit containing a secondary amine or primary amine structural unit with a reactive functional group of the monomer A and the carboxyl end group structural unit containing a reactive functional group of the monomer B.
The structure of the monomer A of the protective coating of the specific embodiment of the invention is shown as the formula (IV),
Figure BDA0002531765670000051
wherein X is a connecting bond, an oxygen atom or a carbonyl group, R1Is C1-C10Alkylene of (C)1-C10A halogen atom-substituted hydrocarbylene group of R2、R3And R4Each independently selected from hydrogen atom, halogen atom, C1-C10A hydrocarbon group of1-C10A halogen atom-substituted hydrocarbon group of (2), C1-C10Hydrocarbyloxy group of (C)1-C10Halogen atom-substituted hydrocarbyloxy group of (2), C1-C10With a hydrocarbon acyloxy group or C1-C10The halogen atom of (a) is substituted with a hydrocarbon acyloxy group. In some embodiments of the invention, the alkylene group is a saturated alkylene group, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, and the like, and in other embodiments of the invention, the alkylene group is an unsaturated alkenylene, alkynylene, or aralkylene group. In some embodiments of the invention, the hydrocarbyl group is a saturated alkyl group, e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like, and in other embodiments of the invention, the hydrocarbyl group is an unsaturated alkenyl, alkynyl, or aromatic hydrocarbyl group. In some embodiments of the invention, the hydrocarbyloxy group is a saturated alkoxy group, e.g., methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, and the like, and in other embodiments of the invention, the hydrocarbyloxy group is an unsaturated alkenyloxy, alkynyloxy, or arenyloxy group. In some embodiments of the invention, the hydrocarbon acyloxy group is a saturated alkanoyloxy group, e.g., formyloxy, acetyloxy, propionyloxy, butyryloxy, valeryloxy, hexanoyloxy, and the like, and in other embodiments of the invention, the hydrocarbon acyloxy group is an unsaturated alkenoyloxy, alkynyloxy, or arenoyloxy group. In some embodiments of the invention, X is a connecting bond, R1Is C1-C10Alkylene of (2), especially ethylene, propylene or butylene, R2、R3And R4Are each independently C1-C10In particular methoxy, ethoxy or propoxy.
In the protective coating of the specific embodiment of the invention, the structure of the monomer B is shown as a formula (V),
Figure BDA0002531765670000052
wherein R is5、R6And R7Each independently selected from hydrogen atom, halogen atom, C1-C10Or C is a hydrocarbon group1-C10By halogen atoms ofSubstituted hydrocarbon radical, Y is a connecting bond, C1-C10Alkylene or C1-C10The halogen atom-substituted alkylene group of (1). In some embodiments of the invention, the alkylene group is a saturated alkylene group, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, and the like, and in other embodiments of the invention, the alkylene group is an unsaturated alkenylene, alkynylene, or aralkylene group. In some embodiments of the invention, the hydrocarbyl group is a saturated alkyl group, e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like, and in other embodiments of the invention, the hydrocarbyl group is an unsaturated alkenyl, alkynyl, or aryl group. In some embodiments of the invention, R is5、R6And R7Each independently selected from hydrogen atom or methyl group, in particular R5、R6Is a hydrogen atom, R7Is a hydrogen atom or a methyl group, and Y is a connecting bond.
The protective coating according to embodiments of the present invention may be selected from one or more of fluoroalkanes, fluoroalkenes, and fluoroalkynes, and specific examples of the fluoroalkanes include one or more of fluoroalkanes, fluoroalkenes, and fluoroalkynes, such as tetrafluoromethane, hexafluoroethane, octafluoropropane, decafluorobutane, and the like, fluoroolefins such as tetrafluoroethylene, hexafluoropropylene, octafluorobutene, decafluoropentene, or 1H, 2H-perfluoro-1 dodecene, and the like, and fluoroalkynes such as difluoroacetylene, tetrafluoropropyne, or hexafluorobutyne, and the like.
In some embodiments of the protective coatings of the present invention, the fluoroacrylate comprises a fluoroacrylate of the following formula (VI),
Figure BDA0002531765670000061
in the formula (VI), R8、R9And R10Each independently selected from a hydrogen atom, a halogen atom、C1-C10Or a hydrocarbon radical of C1-C10X is an integer of 0, 1 or 2, and y is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20. In some embodiments of the invention, the hydrocarbyl group is a saturated alkyl group, e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like, and in other embodiments of the invention, the hydrocarbyl group is an unsaturated alkenyl, alkynyl, or aryl group. In some embodiments of the invention, R8、R9And R10Each independently selected from a hydrogen atom or a methyl group.
The protective coating of embodiments of the present invention, in some embodiments, is an electronic or electrical component, such as a mobile phone, audio device, laptop computer, Printed Circuit Board (PCB), Printed Circuit Board Array (PCBA), transistor, resistor, or semiconductor chip, among others, and in other embodiments, is a substrate of various other plastics, fabrics, glass, or metals. In some embodiments, the substrate comprises a substrate that has been subjected to a surface pretreatment or pretreatment including, for example, a thermal, oxygen, or plasma surface cleaning treatment, as well as other coating treatments of the surface, and the like.
In the protective coating according to the embodiment of the present invention, the molar ratio of the monomer a based on the amino structural unit to the monomer B based on the carboxyl end group structural unit is 10: 0.1-1: 10, further, the molar ratio of monomer a, based on the amine-group structural units, to monomer B, based on the carboxyl-end-group structural units, is 10: 0.5-1: 5, in particular for example the molar ratio of monomer A based on amine structural units to monomer B based on carboxyl end structural units is 10: 0.5, 10: 1. 10: 2. 10: 3. 10: 4. 10: 5. 10:10, 5:10, etc., said molar amounts of monomer A based on the amine-group structural unit and monomer B based on the carboxyl-end-group structural unit being calculated as the molar amounts of the amine-group structural units of formulae (II) and (III) contained in monomer A and the molar amount of monomer B is calculated as the molar amount of the carboxyl-end-group structural unit contained in monomer B.
In some embodiments, the molar ratio of the sum of monomer a and monomer B to monomer C is 1: 20-20: 1, particularly, the protective performance and the wear resistance are considered, and the molar ratio of the sum of the monomer A and the monomer B to the monomer C is 1: 5-5: 1, further 1: 0.5-1: 3.5.
The protective coating of embodiments of the present invention is formed by plasma polymerization, and has a coating thickness on the order of nanometers, and in some embodiments, has a thickness between 1nm and 1000 nm.
The specific embodiment of the invention also provides a preparation method of the protective coating, which comprises the following steps: providing a substrate, and placing the substrate in a plasma reactor; and gasifying the monomer A, the monomer B and the monomer C, introducing the gasified monomers into a plasma reactor, discharging the plasma, and polymerizing the plasma on the surface of the base material to form a coating. The relevant description for the monomer A, monomer B, fluorohydrocarbon, fluoroacrylate, or fluorosilane, and substrate, etc., is as previously described.
In some embodiments, the monomer a, the monomer B, and the monomer C are gasified and then enter the plasma reactor; in some embodiments, monomer A and monomer B are mixed before being gasified, which facilitates the reaction between the amine and carboxyl groups of monomer A and monomer B, so that the protective coating formed has better protective performance.
The preparation method of the protective coating of the embodiments of the present invention, in some embodiments, the plasma polymerization uses continuous plasma, in some embodiments, to obtain better wear resistance, the plasma polymerization uses pulsed plasma, in some embodiments, the following pulsed plasma polymerization process is used, the substrate is placed in the reaction cavity, the cavity is vacuumized to 1 mtorr-100 torr, the monomer taking part in the reaction enters the cavity in a gaseous state by heating, and the inert gas helium is introduced, the power supply is turned on to generate plasma, thereby chemical vapor deposition is generated on the surface of the substrate, wherein, the temperature in the cavity is controlled to be 20 ℃ to 60 ℃, the monomer gasification temperature is 70 ℃ to 150 ℃, and the gasification is performed under the vacuum condition, the body flow is 10 to 1000 muL/min, in particular 100-200 mu L/min, the plasma discharge mode is radio frequency pulse discharge, the power is 2W-500W, in particular 50W-200W, the pulse frequency is 10Hz-50kHz, in particular 50Hz-500Hz, the pulse duty ratio is 0.1% -80%, in particular 10% -50%, and the plasma discharge time is 100s-20000s, in particular 500s-5000 s. In some embodiments of the present invention, the plasma discharge may be radio frequency discharge, microwave discharge, medium frequency discharge, or electric spark discharge.
Embodiments of the present invention also provide a device having at least a portion of a surface thereof with a protective coating comprising any of the above-described protective coatings, in some embodiments, only the above-described protective coating deposited on a portion of or the entire surface of the device, and in some embodiments, additional coatings deposited on a portion of or the entire surface of the device in addition to the above-described protective coating.
The present invention is further illustrated by the following specific examples.
Examples
Example 1
The first scheme is as follows:
placing circuit boards 1, 2 and 3 in a plasma chamber, vacuumizing the chamber to 8 mTorr, introducing helium gas, enabling the flow rate to be 40sccm, starting plasma discharge, enabling the power supply to be 200W, enabling the pulse duty ratio to be 25%, enabling the pulse frequency to be 500Hz, mixing 3-aminopropyl trimethoxy silane and methacrylic acid, and enabling the mixture and 2-perfluoro octyl ethyl acrylate to be gasified and enter the plasma chamber respectively, wherein the molar ratio of the 3-aminopropyl trimethoxy silane to the methacrylic acid to the 2-perfluoro octyl ethyl acrylate is 10: 1: 33, the flow rate is 220 mu L/min, and the coating time is 7200 s. After the coating is finished, compressed air is filled in to restore the normal pressure of the chamber. And taking out the circuit board sample.
Scheme II:
placing the circuit boards 1 ', 2 ' and 3 ' in a plasma chamber, vacuumizing the chamber to 8 mTorr, introducing helium gas, introducing 40sccm of flow, starting plasma discharge, introducing monomer 2-perfluorooctyl ethyl acrylate to gasify and enter the plasma chamber, wherein the power is 200W, the pulse duty ratio is 25%, the pulse frequency is 500Hz, the flow is 220 muL/min, and the coating time is 7200 s. After the coating is finished, compressed air is filled in to restore the normal pressure of the chamber. And taking out the circuit board sample.
And (3) carrying out abrasion resistance test on the circuit board in the scheme I and the scheme II on an abrasion resistance tester, wherein the friction material is dust-free cloth, the load is 100g, the rotating speed is 50r/min, and the friction times are 50 times. And (3) carrying out water soaking verification after friction, wherein the water soaking verification process is as follows: 1. the power supply provides voltage for the circuit board; 2. soaking the circuit board in water; 3. detecting the current by using a computer; 4. the time to failure (current > 0.6mA) or the test time reached 13min was recorded.
The test results were as follows:
Figure BDA0002531765670000091
example 2
The first scheme is as follows:
placing a flexible substrate sample in a plasma chamber, vacuumizing the chamber to 5 mTorr, introducing helium gas with the flow rate of 40sccm, starting plasma discharge, wherein the power supply power is 25W, the pulse duty ratio is 35%, the pulse frequency is 700Hz, mixing 3-aminopropyl trimethoxy silane and methacrylic acid, and gasifying the mixture and 1H,1H,2H, 2H-perfluorooctanol acrylate respectively into the plasma chamber, wherein the molar ratio of the 3-aminopropyl trimethoxy silane to the methacrylic acid to the 1H,1H,2H, 2H-perfluorooctanol acrylate is 10:2:20, the flow rate is 430microliter/min, and the coating time is 0 s. And after the film coating is finished, filling compressed air to restore the normal pressure in the chamber, and taking out the flexible substrate sample.
Scheme II:
placing a flexible substrate sample in a plasma chamber, vacuumizing the chamber to 5 mTorr, introducing helium gas, enabling the flow rate to be 40sccm, starting plasma discharge, enabling the power supply power to be 25W, the pulse duty ratio to be 35%, the pulse frequency to be 700Hz, gasifying the monomers 1H,1H,2H and 2H-perfluorooctanol acrylate, and enabling the monomers to enter the plasma chamber, wherein the flow rate is 220 mu L/min, and the coating time is 4300 s. And after the film coating is finished, filling compressed air to restore the normal pressure in the chamber, and taking out the flexible substrate sample.
Bending the flexible substrate sample of the first scheme and the second scheme in the same way for 100 times, wherein the film layer on the surface of the sample observed in the first scheme has no obvious change and is consistent with the surface of the part which is not bent; and the film layer peeling phenomenon exists on the surface of the sample in the second scheme.
Example 3
The first scheme is as follows:
placing FPC (flexible printed circuit board) samples 1, 2 and 3 in a plasma chamber, vacuumizing the chamber to 6 mTorr, introducing helium gas, enabling the flow rate to be 45sccm, starting plasma discharge, enabling the power supply power to be 180W, enabling the pulse duty ratio to be 35%, enabling the pulse frequency to be 300Hz, mixing 3-aminopropyl trimethoxy silane and methacrylic acid, and enabling the mixture and 2-perfluoro octyl ethyl acrylate to be gasified and enter the plasma chamber respectively, wherein the molar ratio of the 3-aminopropyl trimethoxy silane to the methacrylic acid to the 2-perfluoro octyl ethyl acrylate is 10:2: 36, the flow rate is 200 mu L/min, and the coating time is 7200 s. And after the film coating is finished, filling compressed air to restore the normal pressure in the chamber, and taking out the FPC sample.
Scheme two is as follows:
placing FPC samples 1 ', 2 ' and 3 ' in a plasma chamber, vacuumizing the chamber to 6 mTorr, introducing helium gas, enabling the flow rate to be 45sccm, starting plasma discharge, enabling the power supply power to be 180W, enabling the pulse duty ratio to be 35%, enabling the pulse frequency to be 300Hz, gasifying monomer 2-perfluorooctyl ethyl acrylate, and enabling the monomer to enter the plasma chamber, wherein the flow rate is 200 mu L/min, and the coating time is 7200 s. And after the film coating is finished, filling compressed air to restore the normal pressure in the chamber, and taking out the FPC sample.
Bending the FPC samples of the scheme I and the scheme II in the same manner for 10 times, and then testing the FPC samples by soaking water, wherein the soaking water testing method is the same as that of the embodiment 1, and the testing conditions are as follows: the time to failure (current greater than 20 μ A) or test time up to 30min was recorded.
The test results were as follows:
Figure BDA0002531765670000111
example 4
The first scheme is as follows:
placing TYPE-C male head and female head 1, 2 and 3 in a plasma chamber, vacuumizing the chamber to 8 mTorr, introducing helium gas, enabling the flow rate to be 40sccm, starting plasma discharge, enabling the power supply power to be 200W, enabling the pulse duty ratio to be 25%, enabling the pulse frequency to be 50Hz, mixing 3-aminopropyl trimethoxy silane and acrylic acid, and enabling the mixture to be gasified with 1H,1H,2H and 2H-perfluorooctanol acrylate respectively to enter the plasma chamber, wherein the molar ratio of the 3-aminopropyl trimethoxy silane to the acrylic acid to the 1H,1H,2H and 2H-perfluorooctanol acrylate is 10:2: 36, the flow rate is 220 mu L/min, and the coating time is 2000 s. And after the film coating is finished, filling compressed air to restore the normal pressure of the chamber. The male and female TYPE-C samples were removed.
Scheme II:
placing the TYPE-C male head and female head 1 ', 2 ' and 3 ' in a plasma chamber, vacuumizing the chamber to 8 mTorr, introducing helium gas, enabling the flow to be 40sccm, starting plasma discharge, enabling the power supply power to be 200W, enabling the pulse duty ratio to be 25%, enabling the pulse frequency to be 50Hz, gasifying the monomer 1H,1H,2H, 2H-perfluorooctanol acrylate into the plasma chamber, enabling the flow to be 220 muL/min, and enabling the coating time to be 2000 s. After the coating is finished, compressed air is filled in to restore the normal pressure of the chamber. The male and female TYPE-C samples were removed.
And (3) testing conditions:
and performing plug-in and plug-out experiments on the TYPE-C male head and the female head of the first scheme and the second scheme, wherein the plug-in and plug-out times are 50 times, and performing power-on test after the plug-in and plug-out experiments are completed. The test was stopped either by recording the time to failure (current greater than 0.1A) or by the time to test reaching 1 hour.
The test results were as follows:
Figure BDA0002531765670000112
Figure BDA0002531765670000121
example 5
The first scheme comprises the following steps:
placing the circuit boards 1, 2 and 3 in a plasma chamber, vacuumizing the chamber to 8 mTorr, introducing helium gas, enabling the flow rate to be 40sccm, starting plasma discharge, enabling the power supply power to be 200W, enabling the pulse duty ratio to be 15%, enabling the pulse frequency to be 500Hz, and respectively gasifying 3-aminopropyl triethoxysilane, methacrylic acid and 2- (perfluorobutyl) ethyl acrylate into the plasma chamber, wherein the molar ratio of the 3-aminopropyl trimethoxysilane to the methacrylic acid to the 2- (perfluorobutyl) ethyl acrylate is 1:1:2, the flow rate is 220 muL/min, and the coating time is 7200 s. After the coating is finished, compressed air is filled in to restore the normal pressure of the chamber. And taking out the circuit board sample.
Scheme II:
placing the circuit boards 1 ', 2 ' and 3 ' in a plasma chamber, vacuumizing the chamber to 8 mTorr, introducing helium gas, introducing 40sccm, starting plasma discharge, introducing 200W of power supply power, 15% of pulse duty ratio and 500Hz of pulse frequency, introducing monomer 2- (perfluorobutyl) ethyl acrylate, gasifying, and introducing the monomer into the plasma chamber, wherein the flow is 220 mu L/min, and the coating time is 7200 s. After the coating is finished, compressed air is filled in to restore the normal pressure of the chamber. And taking out the circuit board sample.
And (3) carrying out an abrasion resistance test on the circuit board boards of the first scheme and the second scheme on an abrasion resistance tester, wherein the friction material is dust-free cloth, the load is 100g, the rotating speed is 50r/min, and the friction times are 50 times. And (3) carrying out water soaking verification after friction, wherein the water soaking verification process is as follows: 1. the power supply provides voltage for the circuit board; 2. soaking the circuit board in water; 3. detecting the current by using a computer; 4. the time to failure (current > 0.6mA) or the test time reached 13min was recorded.
The test results were as follows:
Figure BDA0002531765670000131
although the present invention is disclosed above, the present invention is not limited thereto. Various changes and modifications may be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (19)

1. The protective coating is characterized in that a monomer A, a monomer B and a monomer C are taken as raw materials and are deposited on the surface of a base material through plasma polymerization to form the protective coating;
wherein, the monomer A simultaneously comprises a silicon structural unit of a formula (I) and at least one of an amino structural unit of a formula (II) or a formula (III);
Figure FDA0003624170040000011
-NH- (Ⅱ)-NH2 (Ⅲ)
the monomer B comprises carboxyl end group structural units, the structure of the monomer B is shown as a formula (V),
Figure FDA0003624170040000012
wherein R is5、R6And R7Each independently selected from hydrogen atom, halogen atom, C1-C10Or C is a hydrocarbon group1-C10A halogen atom-substituted hydrocarbon group of (A), Y is a connecting bond, C1-C10Alkylene or C1-C10A halogen atom-substituted hydrocarbylene group of (1);
monomer C is a fluoroacrylate.
2. The protective coating of claim 1, wherein the monomer A has the formula (IV),
Figure FDA0003624170040000013
wherein X is a connecting bond, an oxygen atom or a carbonyl group, R1Is C1-C10Alkylene or C1-C10A halogen atom-substituted hydrocarbylene group of R2、R3And R4Each independently selected from a hydrogen atom, a halogen atom, C1-C10A hydrocarbon group of1-C10A halogen atom-substituted hydrocarbon group of (2), C1-C10Hydrocarbyloxy group of (C)1-C10Halogen atom-substituted hydrocarbyloxy group of (2), C1-C10With a hydrocarbon acyloxy group or C1-C10The halogen atom of (a) is substituted with a hydrocarbon acyloxy group.
3. The protective coating of claim 2, wherein X is a connecting bond and R is1Is C1-C10Alkylene of (A), R2、R3And R4Are each independently C1-C10A hydrocarbyloxy group of (3).
4. The protective coating of claim 3, wherein R is1Is ethylene, propylene or butylene, R2、R3And R4Each independently is methoxy, ethoxy or propoxy.
5. The protective coating of claim 1, wherein R is5、R6And R7Each independently selected from a hydrogen atom or a methyl group, and Y is a bond.
6. The protective coating of claim 5, wherein R is5And R6Is a hydrogen atom, R7Is a hydrogen atom or a methyl group.
7. The protective coating of claim 1 wherein the fluoroacrylate has the structure of formula (VI),
Figure FDA0003624170040000021
wherein R is8、R9And R10Each independently selected from hydrogen atom, halogen atom, C1-C10Or C is a hydrocarbon group1-C10X is an integer of 0 to 2, and y is an integer of 1 to 20.
8. The protective coating of claim 7, wherein R8、R9And R10Each independently selected from a hydrogen atom or a methyl group.
9. The protective coating of claim 1 wherein said substrate is an electronic or electrical component, or a metal.
10. The protective coating according to claim 1, wherein the molar ratio of monomer a based on amine-based structural units to monomer B based on carboxyl-terminated structural units is 10: 0.1-1: 10, respectively.
11. The protective coating of claim 10 wherein the molar ratio of monomer a based on amine-based structural units to monomer B based on carboxyl-terminated structural units is 10: 0.5-1: 5, or more.
12. The protective coating of claim 1 wherein the molar ratio of the sum of monomer a and monomer B to monomer C is 1: 20-20: 1.
13. The protective coating of claim 12 wherein the molar ratio of the sum of monomer a and monomer B to monomer C is 1: 5-5: 1.
14. The protective coating of claim 1, wherein the protective coating thickness ranges from: 1nm-1000 nm.
15. A method of preparing the protective coating of any one of claims 1-14, comprising:
providing a substrate, and placing the substrate in a plasma reactor;
and gasifying the monomer A, the monomer B and the monomer C, introducing the gasified monomers into a plasma reactor, discharging the plasma, and polymerizing the plasma on the surface of the base material to form a coating.
16. The method for preparing a protective coating according to claim 15, wherein the monomer a and the monomer B are mixed before being gasified.
17. The method of producing a protective coating according to claim 15, wherein the plasma is a pulsed plasma.
18. The method of claim 17, wherein the pulsed plasma is generated by applying a pulsed voltage discharge, wherein the pulse power is 2W-500W, the pulse frequency is 10Hz-50kHz, the pulse duty ratio is 0.1% -80%, and the plasma discharge time is 100s-20000 s.
19. A device characterized in that at least part of the surface of the device is provided with a protective coating according to any one of claims 1-14.
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