Hydrophobic and oleophobic film layer and its manufacturing method

Abstract

A specific embodiment of the present disclosure provides a hydrophobic-oleophobic film layer and a method for manufacturing the same. The hydrophobic-oleophobic film layer is manufactured by plasma-enhanced chemical vapor deposition from a perfluoropolyether monomer containing an acrylate group and a monomer having two or more carbon-carbon unsaturated bonds. The hydrophobic-oleophobic film layer has good hydrophobicity, oleophobicity, and hydrophobic stability and double 85 stability, is environmentally friendly, and application of the film layer does not cause biological contamination.

Description

[Technical Field]

[0001] This application is This is a national phase application of the international application PCT / CN2023 / 129204 filed on November 2, 2023. Priority is claimed based on a Chinese patent application filed with the China Patent Office on November 25, 2022, application number 202211490705.7, entitled "Hydrophobic and oleophobic film layer and its manufacturing method," the entire contents of which are incorporated herein by reference.

[0002] FIELD OF THE DISCLOSURE The present disclosure relates to the field of surface modification, and in particular to hydrophobic and oleophobic film layers and methods for making the same. [Background technology]

[0003] Hydrophobic and oleophobic film layers can be applied to substrates to achieve self-cleaning, antifouling, and anticorrosion properties. Because the surface tension of water (72 mN / m) is much higher than that of oil (25-40 mN / m), producing an oleophobic surface is more challenging than producing a hydrophobic surface. Oil can spread on almost any fluorine-free substrate. Only when the surface energy of the substrate or coating is lower than that of the oil will the substrate or coating exhibit varying degrees of oleophobicity. Therefore, fluorocarbon groups (-CF2 and -CF3) can lower the surface tension of materials more effectively than hydrocarbons.

[0004] Long-chain perfluoroalkyl compounds (C n F 2n+1 LCPFAs (-R, n≧7, LCPFAs) are widely used to produce hydrophobic and oleophobic surfaces. However, LCPFAs are bioaccumulative and toxic to the environment, humans, and wildlife, and are difficult to degrade in nature, so their production and use have been gradually phased out. The EU POPs regulation calls for the ban of the use of perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), and their derivatives.

[0005] Perfluoropolyethers (PFPEs) can be used as a substitute for long-chain perfluoroalkyl substances. The perfluorocarbon chains in their main chains are interrupted by oxygen atoms, and they do not contain long fluorocarbon chain alkyl groups, making them non-toxic and non-bioccumulative. Furthermore, their surface energy is low at 10-14 mN / m, and modification based on perfluoropolyether segments can be used to prepare film layers with hydrophobic and oleophobic properties.

[0006] However, although the film layer prepared by modification with perfluoropolyether has hydrophobic and oleophobic properties, due to the excellent flexibility of the perfluoropolyether segments, when it comes into contact with polar molecules such as water, the perfluoropolyether chains on the surface of the film layer are likely to rearrange, exposing the polar ether bonds to the air surface, reducing the hydrophobicity of the film layer and preventing it from having stable hydrophobicity for practical use.

[0007] Therefore, it is necessary to produce a film layer with good hydrophobicity, oleophobicity and hydrophobicity stability. Summary of the Invention

[0008] A specific embodiment of the present disclosure provides a hydrophobic-oleophobic film layer, the hydrophobic-oleophobic film layer being a plasma polymerized coating formed by contacting a substrate with a plasma of monomer α and monomer β, where monomer α has the structure of formula (1): JPEG2025537384000029.jpg2485(1) In formula (1), R1, R2, and R3 are each independently selected from a C1-C4 hydrocarbon group or a hydrogen atom, R4 is selected from a C1-C4 perfluoroalkyl group or a fluorine atom, L1 is a linking group, m is an integer of 1 or more, and of the m repeating units, n in each repeating unit is independently selected from an integer of 1 or more, and the monomer β has two or more carbon-carbon unsaturated bonds.

[0009] Optionally, the carbon-carbon unsaturated bond of the monomer β has the structure of formula (2): JPEG2025537384000030.jpg2535(2) In formula (2), Z1, Z2 and Z3 are each independently selected from a hydrogen atom or a C1 to C4 alkyl group.

[0010] Optionally, the monomer β has the structure of formula (3): JPEG2025537384000031.jpg2376(3) In formula (3), R5, R6, R7, R8, R9 and R 10 are each independently selected from a hydrogen atom or a C1 to C4 alkyl group, and R 11 is C2~C 10 wherein x is an integer of 1 to 10, and the substituent of the substituted alkylene group is a C1 to C4 alkyl group or a C1 to C4 hydroxyalkyl group.

[0011] Optionally, said R5, R6, R7, R8, R9 and R 10 are each independently selected from a hydrogen atom or a methyl group.

[0012] Optionally, the monomer β is selected from at least one of ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, 1,6-hexanediol dimethacrylate, 1,6-hexanediol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, polypropylene glycol diacrylate, 1,5-pentanediol diacrylate, dipropylene glycol diacrylate, or tripropylene glycol diacrylate.

[0013] Optionally, the monomer β has the structure of formula (4): JPEG2025537384000032.jpg7590(4) In formula (4), R 12 is C1~C 10 C1-C substituted with alkyl or hydroxy groups 10 is an alkyl group of the formula R 13 , R 14 and R 15 are independently C1 to C 10 and R 16 , R 17 and R 18 are independent of each other, C2 to C 10 and R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 and R 27are each independently selected from a hydrogen atom or a C1-C4 alkyl group, and y1, y2, and y3 are each independently selected from integers of 0-10.

[0014] Optionally, in formula (4), the R 12 is a C1-C4 alkyl group or a C1-C4 hydroxyalkyl group, and the R 13 , R 14 and R 15 are each independently selected from C1 to C4 alkylene groups, 16 , R 17 and R 18 are each independently selected from C2 to C4 alkylene groups, and 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 and R 27 are each independently selected from a hydrogen atom or a methyl group, and y1, y2, and y3 are each independently selected from integers of 0 to 2.

[0015] Optionally, the monomer β is selected from at least one of trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane triacrylate.

[0016] Optionally, the monomer β is selected from at least one of pentaerythritol tetraacrylate, polydipentaerythritol pentaacrylate, polydipentaerythritol hexaacrylate, triallyl cyanurate, triallylamine, divinylbenzene, diethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,4-butanediol divinyl ether, pentaerythritol triallyl ether, 2,6-dimethyl-2,4,6-octatriene, 1,2,4-trivinylcyclohexane, and 1,4-cyclohexanedimethanol divinyl ether.

[0017] Optionally, the monomer β is selected from one or more of diethylene glycol diacrylate, trimethylolpropane triacrylate, and 1,6-hexanediol diacrylate.

[0018] Optionally, the molar ratio of the monomer α to the monomer β is 0.5:9.5 to 9.5:0.5.

[0019] Optionally, the molar ratio of the monomer α to the monomer β is 5:5 to 9.5:0.5.

[0020] Optionally, in formula (1), R1, R2 and R3 are each independently selected from a methyl group or a hydrogen atom.

[0021] Optionally, in formula (1), R1 is a methyl group, and R2 and R3 are hydrogen atoms.

[0022] Optionally, the weight average molecular weight of said monomer α is 1000 or greater.

[0023] Optionally, in formula (1), L1 is selected from substituted or unsubstituted C1 to C4 alkylene groups.

[0024] Optionally, the substituted substituent is one or more of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a heterocyclyl group, a carboxy group, a carboxylate group, a carboxylic ester group, a carbamate group, an alkoxy group, a ketone group, an aldehyde group, an amine group, an amide group, a hydroxy group, a nitrile group, a nitroso group, and a halogen.

[0025] Optionally, in formula (1), L1 is a perfluoroalkylene group.

[0026] Optionally, the monomer α has the structure shown in formula (5): JPEG2025537384000033.jpg26123(5) In formula (5), a is an integer of 1 or more, and L2 is selected from a bond, a substituted methylene group or ethylene group, or an unsubstituted methylene group or ethylene group.

[0027] Optionally, the monomer α has the structure shown in formula (6): JPEG2025537384000034.jpg22121(6) In formula (6), b is an integer of 1 or more, c is an integer of 1 or more, and L3 is selected from a bond or a substituted or unsubstituted C1 to C3 alkylene group.

[0028] Optionally, the monomer α has the structure shown in formula (7): JPEG2025537384000035.jpg22114(7) In formula (7), d is an integer of 1 or more, e is an integer of 1 or more, and L4 is selected from a bond or a substituted or unsubstituted C1 to C3 alkylene group.

[0029] Optionally, the monomer α has the structure shown in formula (8): JPEG2025537384000036.jpg21117(8) In formula (8), f is an integer of 1 or more, and L5 is selected from a bond, a substituted or unsubstituted methylene group, or a substituted or unsubstituted ethylene group.

[0030] Optionally, the hydrophobic and oleophobic film layer has a water contact angle of 95 o The hydrophobic and oleophobic film layer has a contact angle of 60°C with n-hexadecane. o That's all.

[0031] Optionally, the hydrophobic and oleophobic film layer has a water contact angle of 108 o The hydrophobic and oleophobic film layer has a contact angle of 65°C with n-hexadecane. o That's all.

[0032] Specific embodiments of the present disclosure further provide a device, at least a portion of the surface of the device having any of the hydrophobic and oleophobic film layers described above.

[0033] A specific embodiment of the present disclosure further provides a method for manufacturing the hydrophobic and oleophobic film layer described above, the method comprising: placing a substrate in a plasma reaction chamber; and vaporizing monomer α and monomer β and then introducing them into the plasma reaction chamber, initiating plasma discharge, and chemical vapor depositing plasma of the monomer α and monomer β on the surface of the substrate to form the hydrophobic and oleophobic film layer.

[0034] Optionally, vaporizing the monomer α and the monomer β and then introducing them into the plasma reaction chamber includes dissolving the monomer α, the fluorine-containing solvent, and the polymerization inhibitor in one another and then adding them to a monomer tank 1, and adding the monomer β to a monomer tank 2; and heating the monomer tank 1 and the monomer tank 2 to vaporize the monomer α and the monomer β and then introducing them into the plasma reaction chamber, respectively.

[0035] Optionally, the gas flow rate introduced from the monomer tank 1 into the plasma reaction chamber is 10-2000 μL / min, and the gas flow rate introduced from the monomer tank 2 into the plasma reaction chamber is 10-2000 μL / min.

[0036] Optionally, the mass of the polymerization inhibitor is 0.1% to 1% of the mass of the monomer α.

[0037] Optionally, a polymerization inhibitor is further added to the monomer tank 2, and the mass of the polymerization inhibitor is 0.1% to 1% of the mass of the monomer β.

[0038] Optionally, the weight ratio of the monomer α to the fluorine-containing solvent is 1:9 to 9:1.

[0039] Optionally, the fluorine-containing solvent is a fluorocarbon solvent, and the fluorocarbon solvent comprises one or more of methyl perfluorobutyl ether, ethyl perfluorobutyl ether, 3-methoxyperfluorohexane, perfluorobutyl ethyl propyl ether, perfluoropolyether oil, hexafluoropropylene oxide dimer, hexafluoropropylene oxide trimer, perfluorotriethylamine, perfluorotripropylamine, perfluorotributylamine, 3M Electronically Fluorinated Fluid 7100, 3M Electronically Fluorinated Fluid 7200, 3M Electronically Fluorinated Fluid 7300, 3M Electronically Fluorinated Fluid 7500, and 3M Electronically Fluorinated Fluid 7700.

[0040] Optionally, the polymerization inhibitor comprises one or more of hydroquinone, p-benzoquinone, methylhydroquinone, p-hydroxyanisole, 2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, and 2,6-di-t-butyl-p-cresol.

[0041] Optionally, the plasma discharge is a continuous discharge, with a discharge power of 10 to 300 W and a discharge time of 60 to 36000 s.

[0042] Optionally, the plasma discharge is a pulse discharge, with a discharge power of 10 to 400 W, a pulse duty ratio of 0.1% to 80%, a pulse frequency of 10 to 500 Hz, and a discharge time of 200 to 36000 s.

[0043] Optionally, the method for producing the hydrophobic and oleophobic film layer further comprises, prior to the chemical vapor deposition, pretreating the substrate by evacuating to a pressure of 10 to 200 mTorr, introducing a mixed gas of one or more of He, Ar, and O2, and initiating plasma discharge.

[0044] Optionally, the plasma discharge method comprises electrodeless discharge, single electrode discharge, dual electrode discharge or multi-electrode discharge.

[0045] Compared with the prior art, the technical solutions of the embodiments of the present disclosure have the following beneficial effects:

[0046] In a specific embodiment of the present disclosure, the hydrophobic-oleophobic film layer is prepared by plasma enhanced chemical vapor deposition from a perfluoropolyether monomer containing a (meth)acrylate group and a monomer having two or more carbon-carbon unsaturated bonds, and the hydrophobic-oleophobic film layer has a water contact angle of 95°C or more. o The hydrophobic and oleophobic film layer has a contact angle of 60°C with n-hexadecane. o In some specific embodiments, the hydrophobic and oleophobic film layer has a water contact angle of 108 o The hydrophobic and oleophobic film layer has a contact angle of 65°C with n-hexadecane. o That's all.

[0047] The hydrophobic and oleophobic film layer provided in a specific embodiment of the present disclosure has a stable water contact angle and a gradual rate of decrease under conditions of a temperature of 85°C and a humidity of 85% RH, and exhibits good hydrophobic and oleophobic stability. [Brief explanation of the drawings]

[0048] [Figure 1]FIG. 1 is a graph showing the results of a double 85 test for Example 1, Example 2, and Comparative Example 1 according to a specific embodiment of the present disclosure. [Figure 2] FIG. 2 is a graph showing the results of the Double 85 test for Examples 3 to 7 in a specific embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0049]

[0023] Specific embodiments of the present disclosure will be described in detail below. This description is illustrative and is used only to explain the present disclosure, and should not be construed as limiting the present disclosure.

[0050] To achieve hydrophobic and oleophobic effects on the surface of a substrate, device, etc., while maintaining hydrophobic and oleophobic stability and avoiding environmental issues, a specific embodiment of the present disclosure provides a hydrophobic and oleophobic film layer, which is a plasma-polymerized coating formed by contacting a substrate with a plasma of monomer α and monomer β, where monomer α has the structure of Formula (1): JPEG2025537384000037.jpg2695(1) In formula (1), R1, R2, and R3 are each independently selected from a C1-C4 hydrocarbon group or a hydrogen atom, R4 is selected from a C1-C4 perfluoroalkyl group or a fluorine atom, L1 is a linking group, m is an integer of 1 or more, and of the m repeating units, n in each repeating unit is independently selected from an integer of 1 or more, and the monomer β has two or more carbon-carbon unsaturated bonds.

[0051] In the hydrophobic-oleophobic film layer of a specific embodiment of the present disclosure, the inventors have found through research that a hydrophobic-oleophobic film layer formed by plasma-enhanced chemical vapor deposition using a monomer α of formula (1) and a monomer β having two or more carbon-carbon unsaturated bonds has excellent hydrophobic-oleophobic effect and hydrophobic-oleophobic stability. Plasma polymerization of monomer β and monomer α improves the crosslink density of the polymer, restricts the rearrangement of the perfluoropolyether chains, and improves hydrophobic stability.

[0052] In the hydrophobic-oleophobic film layer of the specific embodiment of the present disclosure, in some specific embodiments, the carbon-carbon unsaturated bond of the monomer β has the structure of formula (2). JPEG2025537384000038.jpg2942(2) In formula (2), Z1, Z2 and Z3 are each independently selected from a hydrogen atom or a C1 to C4 alkyl group.

[0053] In the hydrophobic and oleophobic film layer of the specific embodiment of the present disclosure, in some specific embodiments, Z1 in formula (2) is selected from a hydrogen atom or a methyl group, and Z2 and Z3 are hydrogen atoms.

[0054] In the hydrophobic-oleophobic film layer of specific embodiments of the present disclosure, in some specific embodiments, the monomer β has a structure of formula (3). JPEG2025537384000039.jpg2993(3) In formula (3), R5, R6, R7, R8, R9 and R 10 are each independently selected from a hydrogen atom or a C1 to C4 alkyl group, and R 11 is C2~C 10 The substituent of the substituted alkylene group is a C1-C4 alkyl group or a C1-C4 hydroxyalkyl group. x is an integer of 1-10.

[0055] In the hydrophobic and oleophobic film layer of the specific embodiments of the present disclosure, in some specific embodiments, R5, R6, R7, R8, R9 and R 10 are each independently selected from a hydrogen atom or a methyl group, and in some specific embodiments, R and R are each independently selected from a hydrogen atom or a methyl group, and R, R, R, and R 10 is a hydrogen atom.

[0056] In the hydrophobic and oleophobic film layer of the specific embodiments of the present disclosure, in some specific embodiments, R5, R6, R7, R8, R9 and R 10 is a hydrogen atom, and R 11 is an ethylene group and x is 2.

[0057] In the hydrophobic and oleophobic film layer of the specific embodiments of the present disclosure, in some specific embodiments, R5, R6, R7, R8, R9 and R 10 is a hydrogen atom, and R 11 is a hexamethylene group and x is 1.

[0058] In some specific embodiments of the hydrophobic-oleophobic film layer of the present disclosure, the monomer β is selected from at least one of ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, 1,6-hexanediol dimethacrylate, 1,6-hexanediol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, polypropylene glycol diacrylate, 1,5-pentanediol diacrylate, dipropylene glycol diacrylate, and tripropylene glycol diacrylate.

[0059] In the hydrophobic-oleophobic film layer of specific embodiments of the present disclosure, in some specific embodiments, the monomer β has a structure of formula (4). JPEG2025537384000040.jpg7895(4) In formula (4), R 12 is C1~C 10 C substituted with alkyl or hydroxy groups 1~ C 10 is an alkyl group of the formula R 13 , R 14 and R 15 are independently C1 to C 10 and R 16 , R 17 and R 18 are independent of each other, C2 to C 10 and R 19 , R 20 , R 21 , R 22 , R23 , R 24 , R 25 , R 26 and R 27 are each independently selected from a hydrogen atom or a C1-C4 alkyl group, and y1, y2, and y3 are each independently selected from integers of 0-10.

[0060] In the hydrophobic and oleophobic film layer of the specific embodiment of the present disclosure, in some specific embodiments, in formula (4), 12 is a C1-C4 alkyl group or a C1-C4 hydroxyalkyl group, and R 13 , R 14 and R 15 are each independently selected from C1 to C4 alkylene groups, and R 16 , R 17 and R 18 are each independently selected from C2 to C4 alkylene groups, and R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 and R 27 are each independently selected from a hydrogen atom or a methyl group, and y1, y2, and y3 are each independently selected from integers of 0 to 2.

[0061] In the hydrophobic and oleophobic film layer of the specific embodiment of the present disclosure, in some specific embodiments, in formula (4), 12 is an ethyl group, and R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 and R 27 is a hydrogen atom, and R 13 , R 14 and R 15 is a methyl group, and y1, y2 and y3 are 0.

[0062] In some specific embodiments of the hydrophobic-oleophobic film layer of the present disclosure, the monomer β is selected from at least one of trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane triacrylate.

[0063] In some specific embodiments of the hydrophobic-oleophobic film layer of the present disclosure, the monomer β is selected from at least one of pentaerythritol tetraacrylate, polydipentaerythritol pentaacrylate, polydipentaerythritol hexaacrylate, triallyl cyanurate, triallylamine, divinylbenzene, diethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,4-butanediol divinyl ether, pentaerythritol triallyl ether, 2,6-dimethyl-2,4,6-octatriene, 1,2,4-trivinylcyclohexane, and 1,4-cyclohexanedimethanol divinyl ether.

[0064] In some specific embodiments of the hydrophobic-oleophobic film layer of the present disclosure, the monomer β is selected from one or more of diethylene glycol diacrylate, trimethylolpropane triacrylate, and 1,6-hexanediol diacrylate.

[0065] In the hydrophobic-oleophobic film layer of a specific embodiment of the present disclosure, the molar ratio of the monomer α to the monomer β is related to the hydrophobicity, oleophobicity, and hydrophobic-oleophobic stability of the hydrophobic-oleophobic film layer, and therefore can be set according to the requirements for water contact angle and oil contact angle in actual applications. In some specific embodiments, the molar ratio of the monomer α to the monomer β is 0.5:9.5 to 9.5:0.5, and specifically may be, for example, 0.5:9.5, 3:7, 1:9, 5:5, 7:3, 9:1, or 9.5:0.5.

[0066] In the hydrophobic-oleophobic film layer of the specific embodiment of the present disclosure, in some specific embodiments, the molar ratio of the monomer α to the monomer β is 3:7 to 9.5:0.5.

[0067] In the hydrophobic-oleophobic film layer of the specific embodiment of the present disclosure, in some specific embodiments, the molar ratio of the monomer α to the monomer β is 5:5 to 9.5:0.5.

[0068] In some specific embodiments of the hydrophobic-oleophobic film layer of the present disclosure, the monomer α has a structure of formula (1), where R1, R2, and R3 are each independently selected from a methyl group or a hydrogen atom. In some specific embodiments, in formula (1), R1 is a methyl group, and R2 and R3 are hydrogen atoms.

[0069] In some specific embodiments of the hydrophobic-oleophobic film layer of the present disclosure, in order to ensure better crosslinking density, the weight-average molecular weight of the monomer α may be 1000 or more, specifically, for example, 1000, 2000, 3000, 4000, or 5000.

[0070] In some specific embodiments of the hydrophobic and oleophobic film layer of the present disclosure, in formula (1), L1 is selected from substituted or unsubstituted C1 to C4 alkylene groups.

[0071] In the hydrophobic and oleophobic film layer of specific embodiments of the present disclosure, in some specific embodiments, the substituted substituent is one or more of alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, carboxy, carboxylate, carboxylic acid ester, carbamate, alkoxy, ketone, aldehyde, amine, amide, hydroxy, nitrile, nitroso, and halogen. In some specific embodiments, L is a linear or branched perfluoroalkylene group. In some specific embodiments, L is a perfluoroalkylene group.

[0072] In the hydrophobic-oleophobic film layer of specific embodiments of the present disclosure, in some specific embodiments, the perfluoropolyether segment comprises a K-type structure, and the monomer α has the structure shown in formula (5). JPEG2025537384000041.jpg26123(5) In formula (5), a is an integer of 1 or more, L2 is selected from a bond, a substituted or unsubstituted methylene group, or a substituted or unsubstituted ethylene group, and the substituted substituent is selected from one or more of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a heterocyclyl group, a carboxy group, a carboxylate ion, a carboxylate ester group, a carbamate group, an alkoxy group, a ketone group, an aldehyde group, an amine group, an amide group, a hydroxy group, a nitrile group, a nitroso group, and a halogen.

[0073] In the hydrophobic-oleophobic film layer of the specific embodiment of the present disclosure, in some specific embodiments, the perfluoropolyether segment comprises a Y-type structure, and the monomer α has a structure shown in formula (6). JPEG2025537384000042.jpg22121(6) In formula (6), b is an integer of 1 or more, c is an integer of 1 or more, L3 is selected from a bond and a substituted or unsubstituted C1 to C3 alkylene group, and the substituted substituent is selected from one or more of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a heterocyclyl group, a carboxy group, a carboxylate ion, a carboxylate ester group, a carbamate group, an alkoxy group, a ketone group, an aldehyde group, an amine group, an amide group, a hydroxy group, a nitrile group, a nitroso group, and a halogen.

[0074] In the hydrophobic-oleophobic film layer of specific embodiments of the present disclosure, in some specific embodiments, the perfluoropolyether segment comprises a Z-type structure, and the monomer α has a structure shown in formula (7). JPEG2025537384000043.jpg22114(7) In formula (7), d is an integer of 1 or more, e is an integer of 1 or more, L4 is selected from a bond or a substituted or unsubstituted C1 to C3 alkylene group, and the substituted substituent is selected from one or more of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a heterocyclyl group, a carboxy group, a carboxylate ion, a carboxylate ester group, a carbamate group, an alkoxy group, a ketone group, an aldehyde group, an amine group, an amide group, a hydroxy group, a nitrile group, a nitroso group, and a halogen.

[0075] In the hydrophobic-oleophobic film layer of specific embodiments of the present disclosure, in some specific embodiments, the perfluoropolyether segment comprises a D-type structure, and the monomer α has the structure shown in formula (8). JPEG2025537384000044.jpg21117(8) In formula (8), f is an integer of 1 or more, L5 is selected from a bond, a substituted or unsubstituted methylene group, or a substituted or unsubstituted ethylene group, and the substituted substituent is selected from one or more of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a heterocyclyl group, a carboxy group, a carboxylate ion, a carboxylate ester group, a carbamate group, an alkoxy group, a ketone group, an aldehyde group, an amine group, an amide group, a hydroxy group, a nitrile group, a nitroso group, and a halogen.

[0076] In some specific embodiments of the hydrophobic and oleophobic film layer of the present disclosure, in formulas (5) to (8), R1 is a methyl group.

[0077] In some specific embodiments of the hydrophobic-oleophobic film layer of the present disclosure, the hydrophobic-oleophobic film layer has a water contact angle of 95°C or less. o The hydrophobic and oleophobic film layer has a contact angle of 60°C with n-hexadecane. o That's all.

[0078] In some specific embodiments of the hydrophobic-oleophobic film layer of the present disclosure, the hydrophobic-oleophobic film layer has a water contact angle of 108 o The hydrophobic and oleophobic film layer has a contact angle of 65°C with n-hexadecane. o That's all.

[0079] Specific embodiments of the present disclosure further provide a device, at least a portion of the surface of the device having any of the above-described hydrophobic and oleophobic film layers. In some specific embodiments, the entire surface of the device has the hydrophobic and oleophobic film layer to achieve a stable hydrophobic and oleophobic effect over a long period of time.

[0080] In some specific embodiments of the device of the present disclosure, the device includes electrical components, optical equipment, electronic and electrical components, and the like.

[0081] A specific embodiment of the present disclosure further provides a method for manufacturing any of the above-mentioned hydrophobic and oleophobic film layers, the method including: placing a substrate in a plasma reaction chamber; and vaporizing monomer α and monomer β and then introducing them into the plasma reaction chamber, initiating plasma discharge, and chemical vapor depositing plasma of the monomer α and monomer β on the surface of the substrate to form the hydrophobic and oleophobic film layer.

[0082] In some specific embodiments of the manufacturing method of the specific embodiments of the present disclosure, vaporizing the monomer α and the monomer β and then introducing them into the plasma reaction chamber includes: dissolving the monomer α, the fluorine-containing solvent, and the polymerization inhibitor in one another and then adding them to a monomer tank 1, and adding the monomer β to a monomer tank 2; and heating the monomer tank 1 and the monomer tank 2 to vaporize the monomer α and the monomer β and then introducing them into the plasma reaction chamber, respectively.

[0083] In a manufacturing method according to a specific embodiment of the present disclosure, the molar amount of monomer α relative to monomer β entering the plasma reaction chamber during the coating time is controlled by controlling the flow rate ratio of monomer α to monomer β. The molar ratio of monomer α to monomer β is related to the hydrophobicity, oleophobicity, and hydrophobic-oleophobic stability of the hydrophobic-oleophobic film layer, and therefore the flow rates of monomer α and monomer β can be set according to the actual application requirements of the film layer. In some specific embodiments, the ratio of the gas flow rate introduced into the plasma reaction chamber from monomer tank 1 to the gas flow rate introduced into the plasma reaction chamber from monomer tank 2 is 0.5:9.5 to 9.5:0.5, and specifically may be, for example, 0.5:9.5, 3:7, 1:9, 5:5, 7:3, 9:1, or 9.5:0.5.

[0084] In some specific embodiments of the manufacturing methods of the present disclosure, the ratio of the flow rate of the gas introduced from the monomer tank 1 to the plasma reaction chamber to the flow rate of the gas introduced from the monomer tank 2 to the plasma reaction chamber is 3:7 to 9.5:0.5. In some specific embodiments, the ratio of the flow rate of the gas introduced from the monomer tank 1 to the plasma reaction chamber to the flow rate of the gas introduced from the monomer tank 2 to the plasma reaction chamber is 5:5 to 9.5:0.5.

[0085] In some specific embodiments of the manufacturing methods of the specific embodiments of the present disclosure, the flow rate of the gas introduced from the monomer tank 1 into the plasma reaction chamber is 10 to 2000 μL / min, and specifically may be, for example, 10 μL / min, 15 μL / min, 30 μL / min, 90 μL / min, 100 μL / min, 120 μL / min, 150 μL / min, 180 μL / min, 210 μL / min, 270 μL / min, 285 μL / min, 300 μL / min, 500 μL / min, 1000 μL / min, 1500 μL / min, or 2000 μL / min. In some specific embodiments, the flow rate of the gas introduced from the monomer tank 2 into the plasma reaction chamber is 10 to 2000 μL / min, and specifically may be, for example, 10 μL / min, 15 μL / min, 30 μL / min, 90 μL / min, 100 μL / min, 120 μL / min, 150 μL / min, 180 μL / min, 210 μL / min, 270 μL / min, 500 μL / min, 1000 μL / min, 1500 μL / min, or 2000 μL / min.

[0086] In the manufacturing method of specific embodiments of the present disclosure, since monomer α has a high molecular weight and a certain degree of viscosity, a fluorine-containing solvent is added to ensure smooth introduction of the monomer into the plasma reaction chamber. In some specific embodiments, the fluorine-containing solvent is a fluorocarbon solvent. In some specific embodiments, the fluorocarbon solvent includes one or more of methyl perfluorobutyl ether, ethyl perfluorobutyl ether, 3-methoxyperfluorohexane, perfluorobutyl ethyl propyl ether, perfluoropolyether oil, hexafluoropropylene oxide dimer, hexafluoropropylene oxide trimer, perfluorotriethylamine, perfluorotripropylamine, perfluorotributylamine, 3M Electronic Fluorinated Liquid 7100, 3M Electronic Fluorinated Liquid 7200, 3M Electronic Fluorinated Liquid 7300, 3M Electronic Fluorinated Liquid 7500, and 3M Electronic Fluorinated Liquid 7700.

[0087] In some specific embodiments of the production method of the specific embodiments of the present disclosure, the weight ratio of the monomer α to the fluorine-containing solvent is 1:9 to 9:1, and specifically may be, for example, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 3:7, 1:2, 1:1, 2:1, 7:3, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, or 9:1.

[0088] In the manufacturing method of specific embodiments of the present disclosure, a polymerization inhibitor is added to prevent the monomer α from polymerizing to form a polymer in the monomer tank during the thermal vaporization. In some specific embodiments, the polymerization inhibitor includes one or more of hydroquinone, p-benzoquinone, methylhydroquinone, p-hydroxyanisole, 2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, and 2,6-di-t-butyl-p-cresol.

[0089] In some specific embodiments of the production methods according to the specific embodiments of the present disclosure, the amount of the polymerization inhibitor used is, in mass %, 0.1% to 1% of the amount of the monomer α used, and specifically may be, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1%.

[0090] In the manufacturing method of the specific embodiments of the present disclosure, to prevent the polymerization reaction of the monomer β during the thermal vaporization, in some specific embodiments, a polymerization inhibitor is further added to the monomer tank 2, and the amount of the polymerization inhibitor used is 0.1% to 1% by mass of the amount of the monomer β used, specifically, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1%. In some specific embodiments, the polymerization inhibitor includes one or more of hydroquinone, p-benzoquinone, methylhydroquinone, p-hydroxyanisole, 2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, and 2,6-di-t-butyl-p-cresol.

[0091] In the manufacturing method of the specific embodiments of the present disclosure, in some specific embodiments, the molecular weight of the monomer β is not large, and a polymerization reaction is unlikely to occur during the heating and vaporization, so there is no need to add a polymerization inhibitor.

[0092] In the manufacturing method of the specific embodiments of the present disclosure, in some specific embodiments, the temperature of the reaction chamber during plasma polymerization is 30°C to 60°C, and specifically may be, for example, 30°C, 40°C, 50°C, 55°C, or 60°C.

[0093] In some specific embodiments of the manufacturing methods of the specific embodiments of the present disclosure, the plasma discharge is continuous discharge, and the discharge power is 10 to 300 W, specifically, for example, 10 W, 50 W, 100 W, 200 W, or 300 W. The discharge time is 60 to 36,000 s, specifically, for example, 60 s, 360 s, 1,200 s, 2,400 s, 3,600 s, 7,200 s, or 36,000 s.

[0094] In some specific embodiments of the manufacturing methods of the specific embodiments of the present disclosure, the plasma discharge is pulse discharge, and the discharge power is 10 to 400 W, specifically, for example, 10 W, 50 W, 100 W, 180 W, 200 W, 250 W, 300 W, or 400 W. The pulse duty ratio is 0.1% to 80%, specifically, for example, 0.1%, 1%, 10%, 25%, 35%, 50%, 60%, 70%, or 80%. The pulse frequency is 10 to 500 Hz, specifically, for example, 10 Hz, 100 Hz, 200 Hz, 250 Hz, 300 Hz, or 500 Hz. The discharge time is 200 to 36,000 seconds, and specifically may be, for example, 200 seconds, 360 seconds, 1,200 seconds, 2,400 seconds, 3,600 seconds, 7,200 seconds, or 36,000 seconds.

[0095] In some specific embodiments of the manufacturing method of the specific embodiments of the present disclosure, before the chemical vapor deposition, the substrate is pretreated by evacuating to a vacuum of 10 to 200 mTorr, introducing a mixed gas of one or more of He, Ar, and O, and initiating plasma discharge.

[0096] In some specific embodiments of the manufacturing methods of the specific embodiments of the present disclosure, during pretreatment, the plasma discharge is continuous discharge, and the discharge power is 50 to 600 W, specifically, for example, 50 W, 100 W, 120 W, 200 W, 300 W, 400 W, or 600 W. The discharge time is 60 to 2400 s, specifically, for example, 60 s, 360 s, 600 s, 1200 s, 1800 s, or 2400 s.

[0097] In some specific embodiments of the manufacturing method of the specific embodiments of the present disclosure, during pretreatment, the plasma discharge is pulse discharge, and the discharge power is 10 to 500 W, specifically, for example, 10 W, 50 W, 100 W, 180 W, 200 W, 300 W, or 500 W. The pulse duty ratio is 0.1% to 80%, specifically, for example, 0.1%, 1%, 10%, 25%, 35%, 50%, 60%, 70%, or 80%. The pulse frequency is 10 to 500 Hz, specifically, for example, 10 Hz, 100 Hz, 200 Hz, 250 Hz, 300 Hz, or 500 Hz. The discharge time is 60 Specifically, the time may be, for example, 60 s, 360 s, 600 s, 1200 s, 1800 s, or 2400 s.

[0098] In the manufacturing method of specific embodiments of the present disclosure, in some specific embodiments, the plasma discharge method during pretreatment includes electrodeless discharge, single-electrode discharge, dual-electrode discharge, or multi-electrode discharge. In some specific embodiments, the electrodeless discharge includes radio frequency inductively coupled discharge, micro-discharge, etc. In some specific embodiments, the single-electrode discharge includes corona discharge, plasma jet formed by monopolar discharge, etc. In some specific embodiments, the dual-electrode discharge includes dielectric barrier discharge, exposed electrode radio frequency glow discharge, etc. In some specific embodiments, the multi-electrode discharge includes discharge using a floating electrode as a third electrode, etc.

[0099] In some specific embodiments, the manufacturing method of the specific embodiments of the present disclosure further includes a post-treatment, which includes, after completing the formation of the hydrophobic and oleophobic film layer on the surface of the substrate, introducing clean compressed air or an inert gas into the plasma reaction chamber until the pressure returns to normal, opening the plasma reaction chamber, and removing the substrate. In some specific embodiments, the inert gas is introduced at a flow rate of 5 to 300 sccm. [Example]

[0100] The present invention will be further described below with reference to specific examples. Test method description

[0101] Water contact angle of hydrophobic and oleophobic film layer: Tested according to GB / T 30447-2013 standard.

[0102] Oil contact angle of hydrophobic and oleophobic film layer: Tested using SDC-100 standard contact angle meter to test the contact angle between the film layer and n-hexadecane.

[0103] Double 85 test: A substrate with a hydrophobic / oleophobic film layer formed on its surface was placed in an environment with a temperature of 85°C and a humidity of 85%RH, and the water contact angle and oil contact angle of the hydrophobic / oleophobic film layer were tested at different times to characterize the stability of the hydrophobic / oleophobic properties of the film layer. Example 1

[0104] The Si sheet was placed on a substrate holder in a plasma chamber, the chamber was evacuated to 150 mTorr, helium gas was introduced at a flow rate of 200 sccm, and the chamber temperature was set to 55°C.

[0105] The chamber pressure was maintained at 150 mTorr, the helium gas flow rate was maintained at 200 sccm, and continuous plasma discharge was initiated. The substrate was pretreated with continuous discharge at a discharge power of 300 W for 600 s.

[0106] Next, a homogeneous solution of 3M-7200 fluorinated liquid, monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw≒1000) (SuZhou Chemwells Advanced Materials CO., LTD), and hydroquinone was prepared in a weight ratio of 7:3:0.012 and added to monomer tank 1. Diethylene glycol diacrylate (DEGDA) and hydroquinone were dissolved in a weight ratio of 1:0.004 and then added to monomer tank 2. After vaporizing the monomers in monomer tank 1 and monomer tank 2 at a vaporization temperature of 110°C, the gas from monomer tank 1 was introduced into the plasma chamber at a flow rate of 210 μL / min, and the gas from monomer tank 2 was introduced into the plasma chamber at a flow rate of 90 μL / min, i.e., a flow rate ratio of 7:3. The chamber pressure was maintained at 150 mTorr, the helium gas flow rate was maintained at 200 sccm, and a radio frequency plasma discharge was initiated. The radio frequency energy output method was pulsed to perform plasma chemical vapor deposition on the surface of the substrate. The pulse duty ratio was 50%, the pulse frequency was 300 Hz, the pulse discharge power was 250 W, and the reaction time was 3600 s.

[0107] After coating was completed, compressed air was introduced into the chamber to return it to normal pressure, and the coated substrate was removed and its water contact angle and oil contact angle were tested. The test results are shown in Table 1 below. Then, a double 85 test was performed in a high-temperature and high-humidity environment, and the test results are shown in Figure 1. Example 2

[0108] The Si sheet was placed on a substrate holder in a plasma chamber, the chamber was evacuated to 150 mTorr, helium gas was introduced at a flow rate of 200 sccm, and the chamber temperature was set to 55°C.

[0109] The chamber pressure was maintained at 150 mTorr, the helium gas flow rate was maintained at 200 sccm, and continuous plasma discharge was initiated. The substrate was pretreated with continuous discharge at a discharge power of 300 W for 600 s.

[0110] Next, 3M-7200 fluorinated liquid, monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw≈1000) (SuZhou Chemwells Advanced Materials CO., LTD), and hydroquinone were mixed in a homogeneous solution at a weight ratio of 7:3:0.012 and added to monomer tank 1. Trimethylolpropane triacrylate (TMPTA), diethylene glycol diacrylate (DEGDA), and hydroquinone were dissolved in a weight ratio of 5:5:0.1 and then added to monomer tank 2. After vaporizing the monomers in monomer tank 1 and monomer tank 2 at a vaporization temperature of 110°C, the gas from monomer tank 1 was introduced into the plasma chamber at a flow rate of 210 μL / min, and the gas from monomer tank 2 was introduced into the plasma chamber at a flow rate of 90 μL / min, i.e., a flow rate ratio of 7:3. The chamber pressure was maintained at 150 mTorr, the helium gas flow rate was maintained at 200 sccm, and a radio frequency plasma discharge was initiated. The radio frequency energy output method was pulsed to perform plasma chemical vapor deposition on the surface of the substrate. The pulse duty ratio was 50%, the pulse frequency was 300 Hz, the pulse discharge power was 250 W, and the reaction time was 3600 s.

[0111] After coating was completed, compressed air was introduced into the chamber to return it to normal pressure, and the coated substrate was removed and its water contact angle and oil contact angle were tested. The test results are shown in Table 1 below. Then, a double 85 test was performed in a high-temperature and high-humidity environment, and the test results are shown in Figure 1. Comparative Example 1

[0112] The Si sheet was placed on a substrate holder in a plasma chamber, the chamber was evacuated to 150 mTorr, helium gas was introduced at a flow rate of 200 sccm, and the chamber temperature was set to 55°C.

[0113] The chamber pressure was maintained at 150 mTorr, the helium gas flow rate was maintained at 200 sccm, and continuous plasma discharge was initiated. The substrate was pretreated with continuous discharge at a discharge power of 300 W for 600 s.

[0114] Next, a homogeneous solution of 3M-7200 fluorinated liquid, monofunctional perfluoropolyether (meth)acrylate (molecular weight ≒ 1000) (SuZhou Chemwells Advanced Materials Co., Ltd.), and hydroquinone was prepared in a weight ratio of 7:3:0.012 and added to monomer tank 1. After vaporization at a vaporization temperature of 110 °C, the monomer in monomer tank 1 was introduced into the plasma chamber at a flow rate of 300 μL / min. The chamber pressure was maintained at 150 mTorr, the helium gas flow rate was maintained at 200 sccm, and a radio frequency plasma discharge was initiated. The radio frequency energy output method was pulsed, and plasma chemical vapor deposition was performed on the substrate surface with a pulse duty ratio of 50%, a pulse frequency of 300 Hz, a pulse discharge power of 250 W, and a reaction time of 3600 s.

[0115] After coating was completed, compressed air was introduced into the chamber to return it to normal pressure, and the coated substrate was removed and its water contact angle and oil contact angle were tested. The test results are shown in Table 1 below. Then, a double 85 test was performed in a high-temperature and high-humidity environment, and the test results are shown in Figure 1. Example 3

[0116] The Si sheet was placed on a substrate holder in a plasma chamber, the chamber was evacuated to 100 mTorr, helium gas was introduced at a flow rate of 150 sccm, and the chamber temperature was set to 55°C.

[0117] The chamber pressure was maintained at 100 mTorr, the helium gas flow rate was maintained at 150 sccm, and continuous plasma discharge was initiated. The substrate was pretreated with a discharge power of 400 W and continuous discharge for 600 seconds.

[0118] Next, 3M-7200 fluorinated liquid, monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw ≒ 1000) (SuZhou Chemwells Advanced Materials CO., LTD), and p-hydroxyanisole were mixed in a 7:3:0.015 weight ratio to form a homogeneous solution, which was then added to monomer tank 1. 1,6-hexanediol diacrylate (HDDA) and p-hydroxyanisole were dissolved in a 1:0.005 weight ratio and then added to monomer tank 2. After vaporizing the monomers in monomer tanks 1 and 2 at a vaporization temperature of 110°C, the gas from monomer tank 1 was introduced into the plasma chamber at a flow rate of 285 μL / min, and the gas from monomer tank 2 was introduced into the plasma chamber at a flow rate of 15 μL / min, resulting in a flow rate ratio of 9.5:0.5. The chamber pressure was maintained at 100 mTorr, the helium gas flow rate was maintained at 150 sccm, and a radio frequency plasma discharge was initiated. The radio frequency energy output method was pulsed to perform plasma chemical vapor deposition on the surface of the substrate. The pulse duty ratio was 35%, the pulse frequency was 500 Hz, the pulse discharge power was 200 W, and the reaction time was 3600 s.

[0119] After coating was completed, compressed air was introduced into the chamber to return it to normal pressure, and the coated substrate was removed and its water contact angle and oil contact angle were tested. The test results are shown in Table 1 below. Then, a double 85 test was performed in a high-temperature and high-humidity environment, and the test results are shown in Figure 2. Example 4

[0120] The Si sheet was placed on a substrate holder in a plasma chamber, the chamber was evacuated to 100 mTorr, helium gas was introduced at a flow rate of 150 sccm, and the chamber temperature was set to 55°C.

[0121] The chamber pressure was maintained at 100 mTorr, the helium gas flow rate was maintained at 150 sccm, and continuous plasma discharge was initiated. The substrate was pretreated with a discharge power of 400 W and continuous discharge for 600 seconds.

[0122] Next, a homogeneous solution of 3M-7200 fluorinated liquid, monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw ≒ 1000) (SuZhou Chemwells Advanced Materials CO., LTD), and p-hydroxyanisole was prepared in a weight ratio of 7:3:0.015 and added to monomer tank 1. 1,6-hexanediol diacrylate (HDDA) and p-hydroxyanisole were dissolved in a weight ratio of 1:0.005 and then added to monomer tank 2. After vaporizing the monomers in monomer tanks 1 and 2 at a vaporization temperature of 110 °C, the gas from monomer tank 1 was introduced into the plasma chamber at a flow rate of 270 μL / min, and the gas from monomer tank 2 was introduced into the plasma chamber at a flow rate of 30 μL / min, resulting in a flow ratio of 9:1. The chamber pressure was maintained at 100 mTorr, the helium gas flow rate was maintained at 150 sccm, and a radio frequency plasma discharge was initiated. The radio frequency energy output method was pulsed to perform plasma chemical vapor deposition on the surface of the substrate. The pulse duty ratio was 35%, the pulse frequency was 500 Hz, the pulse discharge power was 200 W, and the reaction time was 3600 s.

[0123] After coating was completed, compressed air was introduced into the chamber to return it to normal pressure, and the coated substrate was removed and its water contact angle and oil contact angle were tested. The test results are shown in Table 1 below. Then, a double 85 test was performed in a high-temperature and high-humidity environment, and the test results are shown in Figure 2. Example 5

[0124] The Si sheet was placed on a substrate holder in a plasma chamber, the chamber was evacuated to 100 mTorr, helium gas was introduced at a flow rate of 150 sccm, and the chamber temperature was set to 55°C.

[0125] The chamber pressure was maintained at 100 mTorr, the helium gas flow rate was maintained at 150 sccm, continuous plasma discharge was initiated, and the substrate was pretreated with a discharge power of 400 W and continuous discharge for 600 s.

[0126] Next, 3M-7200 fluorinated liquid, monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw ≒ 1000) (SuZhou Chemwells Advanced Materials CO., LTD), and p-hydroxyanisole were mixed in a 7:3:0.015 weight ratio to form a homogeneous solution, which was then added to monomer tank 1. 1,6-hexanediol diacrylate (HDDA) and p-hydroxyanisole were dissolved in a 1:0.005 weight ratio and then added to monomer tank 2. After vaporizing the monomers in monomer tanks 1 and 2 at a vaporization temperature of 110°C, the gas from monomer tank 1 was introduced into the plasma chamber at a flow rate of 210 μL / min, and the gas from monomer tank 2 was introduced into the plasma chamber at a flow rate of 90 μL / min, resulting in a flow rate ratio of 7:3. The chamber pressure was maintained at 100 mTorr, the helium gas flow rate was maintained at 150 sccm, and a radio frequency plasma discharge was initiated. The radio frequency energy output method was pulsed to perform plasma chemical vapor deposition on the surface of the substrate. The pulse duty ratio was 35%, the pulse frequency was 500 Hz, the pulse discharge power was 200 W, and the reaction time was 3600 s.

[0127] After coating was completed, compressed air was introduced into the chamber to return it to normal pressure, and the coated substrate was removed and its water contact angle and oil contact angle were tested. The test results are shown in Table 1 below. Then, a double 85 test was performed in a high-temperature and high-humidity environment, and the test results are shown in Figure 2. Example 6

[0128] The Si sheet was placed on a substrate holder in a plasma chamber, the chamber was evacuated to 100 mTorr, helium gas was introduced at a flow rate of 150 sccm, and the chamber temperature was set to 55°C.

[0129] The chamber pressure was maintained at 100 mTorr, the helium gas flow rate was maintained at 150 sccm, and continuous plasma discharge was initiated. The substrate was pretreated with a discharge power of 400 W and continuous discharge for 600 seconds.

[0130] Next, 3M-7200 fluorinated liquid, monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw ≒ 1000) (SuZhou Chemwells Advanced Materials CO., LTD), and p-hydroxyanisole were mixed in a 7:3:0.015 weight ratio to form a homogeneous solution, which was then added to monomer tank 1. 1,6-hexanediol diacrylate (HDDA) and p-hydroxyanisole were dissolved in a 1:0.005 weight ratio and then added to monomer tank 2. After vaporizing the monomers in monomer tanks 1 and 2 at a vaporization temperature of 110°C, the gas from monomer tank 1 was introduced into the plasma chamber at a flow rate of 150 μL / min, and the gas from monomer tank 2 was introduced into the plasma chamber at a flow rate of 150 μL / min, resulting in a flow ratio of 5:5. The chamber pressure was maintained at 100 mTorr, the helium gas flow rate was maintained at 150 sccm, and a radio frequency plasma discharge was initiated. The radio frequency energy output method was pulsed to perform plasma chemical vapor deposition on the surface of the substrate. The pulse duty ratio was 35%, the pulse frequency was 500 Hz, the pulse discharge power was 200 W, and the reaction time was 3600 s.

[0131] After coating was completed, compressed air was introduced into the chamber to return it to normal pressure, and the coated substrate was removed and its water contact angle and oil contact angle were tested. The test results are shown in Table 1 below. Then, a double 85 test was performed in a high-temperature and high-humidity environment, and the test results are shown in Figure 2. Example 7

[0132] The Si sheet was placed on a substrate holder in a plasma chamber, the chamber was evacuated to 100 mTorr, helium gas was introduced at a flow rate of 150 sccm, and the chamber temperature was set to 55°C.

[0133] The chamber pressure was maintained at 100 mTorr, the helium gas flow rate was maintained at 150 sccm, and continuous plasma discharge was initiated. The substrate was pretreated with a discharge power of 400 W and continuous discharge for 600 seconds.

[0134] Next, 3M-7200 fluorinated liquid, monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw ≒ 1000) (SuZhou Chemwells Advanced Materials CO., LTD), and p-hydroxyanisole were mixed in a 7:3:0.015 weight ratio to form a homogeneous solution, which was then added to monomer tank 1. 1,6-hexanediol diacrylate (HDDA) and p-hydroxyanisole were dissolved in a 1:0.005 weight ratio and then added to monomer tank 2. After vaporizing the monomers in monomer tanks 1 and 2 at a vaporization temperature of 110°C, the gas from monomer tank 1 was introduced into the plasma chamber at a flow rate of 90 μL / min, and the gas from monomer tank 2 was introduced into the plasma chamber at a flow rate of 210 μL / min, resulting in a flow rate ratio of 3:7. The chamber pressure was maintained at 100 mTorr, the helium gas flow rate was maintained at 150 sccm, and a radio frequency plasma discharge was initiated. The radio frequency energy output method was pulsed to perform plasma chemical vapor deposition on the surface of the substrate. The pulse duty ratio was 35%, the pulse frequency was 500 Hz, the pulse discharge power was 200 W, and the reaction time was 3600 s.

[0135] After coating was completed, compressed air was introduced into the chamber to return it to normal pressure, and the coated substrate was removed and its water contact angle and oil contact angle were tested. The test results are shown in Table 1 below. Then, a double 85 test was performed in a high-temperature and high-humidity environment, and the test results are shown in Figure 2.

[0136] [Table 1] Test results for water contact angle and oil contact angle JPEG2025537384000045.jpg52154

[0137] According to the test results in Table 1, the water contact angles and oil (n-hexadecane) contact angles of the hydrophobic and oleophobic film layers of Example 1, Example 2, and Comparative Example 1 are similar. FIG. 1 shows a graph of the double 85 test results for Example 1, Example 2, and Comparative Example 1 according to a specific embodiment of the present disclosure. As can be seen from FIG. 1, the water contact angle of the film layer of Comparative Example 1 decreased significantly from the second day of the double 85 test, while the water contact angles of the film layers of Examples 1 and 2 decreased more gradually. The film layer of Example 2 had better hydrophobic stability than the film layers of Example 1 and Comparative Example 1 due to the addition of trimethylolpropane triacrylate (TMPTA) monomer with three double bonds during production.

[0138] According to the test results in Table 1, in Examples 3 to 7, the water contact angle and oil contact angle of the film layer tended to decrease as the ratio of the gas flow rate of monomer tank 1 to the gas flow rate of monomer tank 2 increased from 9.5:0.5 to 9:1, 7:3, 5:5, and 3:7, and as the ratio of the gas flow rate of monomer tank 2 to the gas flow rate of monomer tank 1 increased. Figure 2 is a graph of the results of the double 85 test for Examples 3 to 7 according to a specific embodiment of the present disclosure. As can be seen from Figure 2, as the ratio of the amount of monomer used in monomer tank 1 to the amount of monomer used in monomer tank 2 decreased, the hydrophobicity of the produced film layer decreased, and the water contact angle also decreased. Furthermore, the water contact angle in the double 85 test decreased gradually, indicating high hydrophobic stability.

[0139] The above description is merely an illustrative example adopted to explain the principles of the present disclosure, and is not used to limit the protection scope of the present disclosure. Those skilled in the art can make various modifications and improvements without departing from the spirit and content of the present disclosure, and these modifications and improvements also fall within the protection scope of the present disclosure.

Claims

1. 1. A plasma-polymerized coating formed by contacting a substrate with a plasma of monomer α and monomer β, wherein monomer α has the structure of formula (1): （１） In formula (1), R 1 , R 2 and R 3 are each independently 1 ~C 4 or a hydrogen atom, and R 4 is C 1 ~C 4 or a fluorine atom, 1 is a linking group; m is an integer of 1 or more, and n in each of the m repeating units is independently selected from integers of 1 or more; A hydrophobic and oleophobic film layer, wherein the monomer β has two or more carbon-carbon unsaturated bonds.

2. 2. The hydrophobic and oleophobic film layer according to claim 1, wherein the carbon-carbon unsaturated bond of the monomer β has a structure represented by formula (2). （２） In formula (2), Z 1 , Z 2 and Z 3 are each independently a hydrogen atom or C 1 ~C 4 The alkyl group is selected from the group consisting of:

3. The hydrophobic and oleophobic film layer according to claim 2 , wherein the monomer β has a structure represented by formula (3): （３） In formula (3), R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are each independently a hydrogen atom or C 1 ~C 4 and R 11 is C 2 ~C 10 wherein x is an integer of 1 to 10; The substituent of the substituted alkylene group is C 1 ~C 4 or an alkyl group of C 1 ~C 4 is a hydroxyalkyl group.

4. The R 5 , R 6 , R 7 , R 8 , R 9 and R 10 The hydrophobic and oleophobic film layer according to claim 3, wherein each of is independently selected from a hydrogen atom or a methyl group.

5. 4. The hydrophobic and oleophobic film layer according to claim 3, wherein the monomer β is selected from at least one of ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, 1,6-hexanediol dimethacrylate, 1,6-hexanediol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, polypropylene glycol diacrylate, 1,5-pentanediol diacrylate, dipropylene glycol diacrylate, and tripropylene glycol diacrylate.

6. The hydrophobic and oleophobic film layer according to claim 2 , wherein the monomer β has a structure represented by formula (4): （４） In formula (4), R 12 is C 1 ~C 10 C substituted with an alkyl group or a hydroxy group 1~ C 10 is an alkyl group of the formula R 13 , R 14 and R 15 are each independently 1 ~C 10 and R 16 , R 17 and R 18 are each independently 2 ~C 10 and R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 and R 27 are each independently a hydrogen atom or C 1 ~C 4 and y1, y2, and y3 are each independently selected from integers of 0 to 10.

7. In formula (4), the R 12 is C 1 ~C 4 or an alkyl group of C 1 ~C 4 is a hydroxyalkyl group represented by the formula: 13 , R 14 and R 15 are each independently 1 ~C 4 and R 16 , R 17 and R 18 are each independently 2 ~C 4 and R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 and R 27 are each independently selected from a hydrogen atom or a methyl group, and y1, y2, and y3 are each independently selected from an integer of 0 to 2.

8. 7. The hydrophobic and oleophobic film layer according to claim 6, wherein the monomer β is selected from the group consisting of trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane triacrylate.

9. 2. The hydrophobic and oleophobic film layer according to claim 1, wherein the monomer β is selected from the group consisting of pentaerythritol tetraacrylate, polydipentaerythritol pentaacrylate, polydipentaerythritol hexaacrylate, triallyl cyanurate, triallylamine, divinylbenzene, diethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,4-butanediol divinyl ether, pentaerythritol triallyl ether, 2,6-dimethyl-2,4,6-octatriene, 1,2,4-trivinylcyclohexane, and 1,4-cyclohexanedimethanol divinyl ether.

10. The hydrophobic and oleophobic film layer according to claim 1, wherein the monomer β is selected from the group consisting of diethylene glycol diacrylate, trimethylolpropane triacrylate, and 1,6-hexanediol diacrylate.

11. 2. The hydrophobic and oleophobic film layer according to claim 1, wherein the molar ratio of the monomer α to the monomer β is 0.5:9.5 to 9.5:0.

5.

12. The hydrophobic and oleophobic film layer according to claim 11, wherein the molar ratio of the monomer α to the monomer β is 5:5 to 9.5:0.

5.

13. In formula (1), the R 1 , R 2 and R 3 The hydrophobic and oleophobic film layer according to claim 1 , wherein each of the groups independently is selected from a methyl group or a hydrogen atom.

14. In formula (1), the R 1 is a methyl group, and the R 2 and R 3 The hydrophobic and oleophobic film layer according to claim 1 , wherein is a hydrogen atom.

15. The hydrophobic and oleophobic film layer according to claim 1 , wherein the weight average molecular weight of the monomer α is 1,000 or more.

16. In formula (1), L 1 is a substituted or unsubstituted C 1 ~C 4 2. The hydrophobic and oleophobic film layer according to claim 1, wherein the alkylene group is selected from the group consisting of:

17. 17. The hydrophobic and oleophobic film layer of claim 16, wherein the substituted substituent is one or more of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a heterocyclyl group, a carboxylate group, a carboxylic acid ester group, a carbamate group, an alkoxy group, a ketone group, an aldehyde group, an amine group, an amide group, a hydroxy group, a nitrile group, a nitroso group, and a halogen.

18. In formula (1), L 1 18. The hydrophobic and oleophobic film layer according to claim 17, wherein is a perfluoroalkylene group.

19. The hydrophobic and oleophobic film layer according to claim 1 , wherein the monomer α has a structure represented by formula (5): （５） In formula (5), a is an integer of 1 or more, and L 2 is selected from a bond, a substituted or unsubstituted methylene group, or a substituted or unsubstituted ethylene group.

20. The hydrophobic and oleophobic film layer according to claim 1 , wherein the monomer α has a structure represented by formula (6): （６） In formula (6), b is an integer of 1 or more, c is an integer of 1 or more, and L 3 is a bond or a substituted or unsubstituted C 1 ~C 3 The alkylene group is selected from the following alkylene groups:

21. The hydrophobic and oleophobic film layer according to claim 1 , wherein the monomer α has a structure represented by formula (7): （７） In formula (7), d is an integer of 1 or more, e is an integer of 1 or more, and L 4 is a bond or a substituted or unsubstituted C 1 ~C 3 The alkylene group is selected from the following alkylene groups:

22. The hydrophobic and oleophobic film layer according to claim 1 , wherein the monomer α has a structure represented by formula (8): （８） In formula (8), f is an integer of 1 or more, and L 5 is selected from a bond, a substituted or unsubstituted methylene group, or a substituted or unsubstituted ethylene group.

23. The water contact angle of the hydrophobic and oleophobic film layer is 95 o or more, and the hydrophobic and oleophobic film layer has an n-hexadecane contact angle of 60 o The hydrophobic and oleophobic film layer according to any one of claims 1 to 22, characterized in that

24. The water contact angle of the hydrophobic and oleophobic film layer is 108 o The hydrophobic and oleophobic film layer has a contact angle of 65°C with n-hexadecane. o The hydrophobic and oleophobic film layer according to any one of claims 1 to 22, characterized in that

25. A method for producing the hydrophobic and oleophobic film layer according to any one of claims 1 to 24, comprising: placing the substrate in a plasma reaction chamber; and introducing the monomer α and the monomer β into the plasma reaction chamber after vaporization, initiating plasma discharge, and chemical vapor deposition of the plasma of the monomer α and the monomer β onto the surface of the substrate to form the hydrophobic and oleophobic film layer; A method for producing a hydrophobic and oleophobic film layer, comprising:

26. Introducing the monomer α and the monomer β into the plasma reaction chamber after vaporization includes: Monomer α, a fluorine-containing solvent, and a polymerization inhibitor are dissolved in each other and then added to a monomer tank 1, and monomer β is added to a monomer tank 2; and heating the monomer tank 1 and the monomer tank 2 to vaporize the monomer α and the monomer β, and then introducing them into the plasma reaction chamber, respectively; 26. The method for producing the hydrophobic and oleophobic film layer according to claim 25, comprising:

27. 27. The method for producing a hydrophobic and oleophobic film layer according to claim 26, wherein the gas flow rate introduced from the monomer tank 1 to the plasma reaction chamber is 10 to 2000 μL / min, and the gas flow rate introduced from the monomer tank 2 to the plasma reaction chamber is 10 to 2000 μL / min.

28. The method for producing a hydrophobic and oleophobic film layer according to claim 26, wherein the mass of the polymerization inhibitor is 0.1% to 1% of the mass of the monomer α.

29. 27. The method for producing a hydrophobic and oleophobic film layer according to claim 26, wherein a polymerization inhibitor is further added to the monomer tank 2, and the mass of the polymerization inhibitor is 0.1% to 1% of the mass of the monomer β.

30. The method for producing a hydrophobic and oleophobic film layer according to claim 26, wherein the weight ratio of the monomer α to the fluorine-containing solvent is 1:9 to 9:

1.

31. 27. The method for producing a hydrophobic and oleophobic film layer according to claim 26, wherein the fluorine-containing solvent is a fluorocarbon solvent, and the fluorocarbon solvent includes one or more of methyl perfluorobutyl ether, ethyl perfluorobutyl ether, 3-methoxyperfluorohexane, perfluorobutyl ethyl propyl ether, perfluoropolyether oil, hexafluoropropylene oxide dimer, hexafluoropropylene oxide trimer, perfluorotriethylamine, perfluorotripropylamine, perfluorotributylamine, 3M Electronically Fluorinated Liquid 7100, 3M Electronically Fluorinated Liquid 7200, 3M Electronically Fluorinated Liquid 7300, 3M Electronically Fluorinated Liquid 7500, and 3M Electronically Fluorinated Liquid 7700.

32. 30. The method for producing a hydrophobic and oleophobic film layer according to claim 26 or 29, wherein the polymerization inhibitor comprises one or more of hydroquinone, p-benzoquinone, methylhydroquinone, p-hydroxyanisole, 2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, and 2,6-di-t-butyl-p-cresol.

33. The method for producing a hydrophobic and oleophobic film layer according to claim 26, wherein the plasma discharge is a continuous discharge, the discharge power is 10 to 300 W, and the discharge time is 60 to 36,000 s.

34. The method for producing a hydrophobic and oleophobic film layer according to claim 26, characterized in that the plasma discharge is a pulse discharge, the discharge power being 10 to 400 W, the pulse duty ratio being 0.1% to 80%, the pulse frequency being 10 to 500 Hz, and the discharge time being 200 to 36,000 s.

35. Furthermore, before the chemical vapor deposition, the chamber is evacuated to 10 to 200 mTorr and filled with gases such as He, Ar, and O. 2 and initiating plasma discharge to pretreat the substrate.

36. The method for producing a hydrophobic and oleophobic film layer according to any one of claims 25 to 35, wherein the plasma discharge method includes electrodeless discharge, single-electrode discharge, double-electrode discharge, or multi-electrode discharge.

37. A device, characterized in that at least a part of its surface is provided with a hydrophobic and oleophobic film layer according to any one of claims 1 to 24.

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