A hydrophobic and oleophobic film layer and preparation method thereof

Abstract

The specific embodiments of the present disclosure provide a hydrophobic and oleophobic film layer and a preparation method thereof. The hydrophobic and oleophobic film layer is prepared by plasma chemical vapor deposition of a perfluoropolyether monomer including an acrylate group and a monomer having two or more carbon-carbon unsaturated bonds. The hydrophobic and oleophobic film layer has good hydrophobicity and oleophobicity, as well as hydrophobic stability and double 85 stability, and is environmentally friendly. The application of the film layer does not cause biological pollution.

Description

Technical Field

[0001] The present disclosure relates to the field of surface modification, and in particular to a hydrophobic and oleophobic film layer and a preparation method thereof. Background Art

[0002] Hydrophobic and oleophobic films can be applied to substrates to achieve surface self-cleaning, anti-fouling and anti-corrosion, etc. The preparation of oleophobic surfaces is more challenging than that of hydrophobic surfaces because the surface tension of water (72mN / m) is much higher than the surface tension of oil (25-40mN / m). Oil can diffuse onto almost any fluorine-free substrate. Only when the surface energy of the substrate or coating is lower than the surface energy of the oil will the substrate or coating exhibit varying degrees of oleophobicity. Therefore, fluorocarbon groups (-CF2 and -CF3) are required to manufacture oleophobic surfaces because they can reduce the surface tension of materials better than hydrocarbons.

[0003] Long-chain perfluoroalkyl compounds (C n F 2n+1 -R, n ≥ 7, LCPFAs) are widely used in the preparation of hydrophobic and oleophobic surfaces. However, due to their bioaccumulation and toxicity to the environment, humans, and wildlife, and their difficulty in degradation in nature, their production and application have been gradually phased out. The EU POPs regulations require the ban on the use of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) and their derivatives.

[0004] 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, do not contain long fluorocarbon chain alkyl groups, are non-bioaccumulative and non-toxic, and their surface energy can be as low as 10-14 mN / m. They can be modified based on the perfluoropolyether chain segments to prepare membrane layers with hydrophobic and oleophobic effects.

[0005] However, although the membrane layer prepared by perfluoropolyether modification has hydrophobic and oleophobic properties, due to the good flexibility of the perfluoropolyether chain segment, the perfluoropolyether chain on the membrane surface is easily rearranged when it comes into contact with polar molecules such as water, exposing the polar ether bonds to the air surface, resulting in a decrease in the hydrophobicity of the membrane layer, and thus it does not have stable hydrophobic properties in practical applications.

[0006] Therefore, it is necessary to prepare a membrane layer with good hydrophobic and oleophobic properties and hydrophobic and oleophobic stability. Summary of the Invention

[0007] The specific embodiment of the present disclosure provides a hydrophobic and oleophobic film layer, wherein the hydrophobic and oleophobic film layer is a plasma-polymerized coating formed by contacting a substrate with plasma of monomer α and monomer β, wherein the monomer α has a structure of formula (1),

[0008]

[0009] In formula (1), R1, R2 and R3 are independently selected from C1-C4 hydrocarbon groups or hydrogen atoms; R4 is selected from C1-C4 perfluorinated alkyl groups or fluorine atoms; L1 is a connecting group; m is an integer not less than 1; in the m repeating units, n of each repeating unit is independently selected from an integer not less than 1; and the monomer β has two or more carbon-carbon unsaturated bonds.

[0010] Optionally, the carbon-carbon unsaturated bond of the monomer β has a structure of formula (2),

[0011]

[0012] In formula (2), Z1, Z2 and Z3 are independently selected from hydrogen atom or C1-C4 alkyl group.

[0013] Optionally, the monomer β has a structure of formula (3),

[0014]

[0015] In formula (3), R5, R6, R7, R8, R9 and R 10 R is independently selected from a hydrogen atom or a C1-C4 alkyl group; 11 C2-C 10 alkylene or substituted alkylene, x is an integer from 1 to 10; the substituent of the substituted alkylene is a C1-C4 alkyl or a C1-C4 hydroxyalkyl.

[0016] Optionally, R5, R6, R7, R8, R9 and R 10 are independently selected from a hydrogen atom or a methyl group.

[0017] 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.

[0018] Optionally, the monomer β has a structure of formula (4),

[0019]

[0020] In formula (4), R 12 C1-C 10 Alkyl, or C 1- C 10 The alkyl group, R 13 、R 14 and R 15 Each independently selected from C1-C 10 Alkylene, R 16 、R 17 and R 18 Each independently selected from C2-C 10 Alkylene, R 19 、R 20 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 and R 27 Each of y1, y2 and y3 is independently selected from a hydrogen atom or a C1-C4 alkyl group, and each of y1, y2 and y3 is independently selected from an integer from 0 to 10.

[0021] Optionally, in formula (4), the R 12 is a C1-C4 alkyl group or a C1-C4 hydroxyalkyl group, wherein R 13 、R 14 and R 15 Each independently selected from C1-C4 alkylene, said R 16 、R 17 and R 18 Each independently selected from C2-C4 alkylene, said R 19 、R 20 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 and R 27 are independently selected from a hydrogen atom or a methyl group, and y1, y2 and y3 are independently selected from an integer from 0 to 2.

[0022] Optionally, the monomer β is selected from at least one of trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane triacrylate.

[0023] 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.

[0024] Optionally, the monomer β is selected from one or more of diethylene glycol diacrylate, trimethylolpropane triacrylate, and 1,6-hexanediol diacrylate.

[0025] Optionally, the molar ratio of the monomer α to the monomer β is 0.5:9.5 to 9.5:0.5.

[0026] Optionally, the molar ratio of the monomer α to the monomer β is 5:5 to 9.5:0.5.

[0027] Optionally, in formula (1), R1, R2 and R3 are independently selected from methyl or hydrogen atoms.

[0028] Optionally, in formula (1), R1 is a methyl group, and R2 and R3 are hydrogen atoms.

[0029] Optionally, the weight average molecular weight of the monomer α is greater than 1000.

[0030] Optionally, in formula (1), L1 is selected from: substituted or unsubstituted C1-C4 alkylene.

[0031] Optionally, the substituted substituent is one or more of the following groups: alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclic, carboxyl, carboxylate, carboxylate, carbamate, alkoxy, ketone, aldehyde, amine, amide, hydroxyl, nitrile, nitrite, and halogen.

[0032] Optionally, in formula (1), L1 is a perfluorinated substituted alkylene group.

[0033] Optionally, the monomer α has a structure shown in formula (5),

[0034]

[0035] In formula (5), a is an integer not less than 1; and L2 is selected from a linking bond, a substituted methylene or ethylene group, or an unsubstituted methylene or ethylene group.

[0036] Optionally, the monomer α has a structure shown in formula (6),

[0037]

[0038] In formula (6), b is an integer not less than 1, c is an integer not less than 1; and L3 is selected from a connecting bond, or a substituted or unsubstituted C1-C3 alkylene group.

[0039] Optionally, the monomer α has a structure shown in formula (7),

[0040]

[0041] In formula (7), d is an integer not less than 1, e is an integer not less than 1; and L4 is a group selected from a connecting bond, or a substituted or unsubstituted C1-C3 alkylene group.

[0042] Optionally, the monomer α has a structure shown in formula (8),

[0043]

[0044] In formula (8), f is an integer not less than 1; and L5 is selected from a linking bond, a substituted or unsubstituted methylene group, or a substituted or unsubstituted ethylene group.

[0045] Optionally, the water contact angle of the hydrophobic and oleophobic film layer is greater than 95°, and the n-hexadecane contact angle of the hydrophobic and oleophobic film layer is greater than 60°.

[0046] Optionally, the water contact angle of the hydrophobic and oleophobic film layer is greater than 108°, and the n-hexadecane contact angle of the hydrophobic and oleophobic film layer is greater than 65°.

[0047] A specific embodiment of the present disclosure further provides a device, wherein at least a portion of the surface of the device has any of the above-mentioned hydrophobic and oleophobic film layers.

[0048] A specific embodiment of the present disclosure also provides a method for preparing any of the above-described hydrophobic and oleophobic film layers, the preparation method comprising: placing a substrate in a plasma reaction chamber; vaporizing monomer α and monomer β and then passing them into the plasma reaction chamber, starting plasma discharge, and chemically vapor depositing the plasma of monomer α and monomer β on the surface of the substrate to form the hydrophobic and oleophobic film layer.

[0049] Optionally, the step of vaporizing monomer α and monomer β and then introducing them into the plasma reaction chamber comprises: dissolving monomer α, a fluorine-containing solvent, and a polymerization inhibitor in each other and then adding them into monomer tank one, and adding monomer β into monomer tank two; heating monomer tank one and monomer tank two to vaporize monomer α and monomer β and then introducing them into the plasma reaction chamber respectively.

[0050] Optionally, the gas flow rate from the monomer tank 1 to the plasma reaction chamber is 10 to 2000 μL / min, and the gas flow rate from the monomer tank 2 to the plasma reaction chamber is 10 to 2000 μL / min.

[0051] Optionally, the mass of the polymerization inhibitor is 0.1% to 1% of the mass of the monomer α.

[0052] 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.

[0053] Optionally, the weight ratio of the monomer α to the fluorine-containing solvent is 1:9 to 9:1.

[0054] Optionally, the fluorine-containing solvent is a fluorocarbon solvent, and the fluorocarbon solvent includes: methyl perfluorobutyl ether, ethyl perfluorobutyl ether, 3-methoxyperfluorohexane, perfluorobutyl ethylpropyl 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 one or more of 3M electronic fluorinated liquid 7700.

[0055] Optionally, the polymerization inhibitor includes one or more of hydroquinone, p-benzoquinone, methylhydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, and 2,6-di-tert-butyl-p-cresol.

[0056] Optionally, the plasma discharge is continuous discharge, the discharge power is 10 to 300 W, and the discharge time is 60 to 36,000 s.

[0057] Optionally, the plasma discharge is a pulse discharge with a discharge power of 10 to 400 W, a pulse duty cycle of 0.1% to 80%, a pulse frequency of 10 to 500 Hz, and a discharge time of 200 to 36,000 s.

[0058] Optionally, the method for preparing the hydrophobic and oleophobic film layer further includes: before the chemical vapor deposition, evacuating to 10-200 mTorr, introducing a mixed gas of one or more of He, Ar, and O2, and starting plasma discharge to pretreat the substrate.

[0059] Optionally, the plasma discharge mode includes: electrodeless discharge, single-electrode discharge, double-electrode discharge or multi-electrode discharge.

[0060] Compared with the prior art, the technical solution of the embodiment of the present disclosure has the following beneficial effects:

[0061] The hydrophobic and oleophobic film provided in the embodiments of the present disclosure is prepared by plasma chemical vapor deposition from a perfluoropolyether monomer including a (meth)acrylate group and a monomer having two or more carbon-carbon unsaturated bonds. The hydrophobic and oleophobic film has a water contact angle of 95° or greater, and an n-hexadecane contact angle of 60° or greater. In some embodiments, the water contact angle of the hydrophobic and oleophobic film is 108° or greater, and the n-hexadecane contact angle of the hydrophobic and oleophobic film is 65° or greater.

[0062] The hydrophobic and oleophobic film layer provided in the specific embodiment of the present disclosure has a stable water contact angle and a slow decreasing rate under the conditions of temperature 85° C. and humidity 85% RH, and has good hydrophobic and oleophobic stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0063] Figure 1 Graph showing the dual 85 test results of Example 1, Example 2, and Comparative Example 1 in the specific embodiments of the present disclosure;

[0064] Figure 2 This is a graph showing the dual 85 test results of Examples 3 to 7 in the specific implementation manner of the present disclosure. DETAILED DESCRIPTION

[0065] The specific embodiments of the present disclosure are described in detail below. This description is exemplary and is only used to explain the present disclosure, and should not be understood as limiting the present disclosure.

[0066] In order to achieve a hydrophobic and oleophobic effect on the surface of a substrate, a device, etc., and to have hydrophobic and oleophobic stability without causing environmental problems, a specific embodiment of the present disclosure provides a hydrophobic and oleophobic film layer, wherein the hydrophobic and oleophobic film layer is a plasma-polymerized coating formed by contacting a substrate with a plasma of monomer α and monomer β, wherein the monomer α has a structure of formula (1),

[0067]

[0068] In formula (1), R1, R2 and R3 are independently selected from C1-C4 hydrocarbon groups or hydrogen atoms; R4 is selected from C1-C4 perfluorinated alkyl groups or fluorine atoms; L1 is a connecting group; m is an integer not less than 1; in the m repeating units, n of each repeating unit is independently selected from an integer not less than 1; and the monomer β has two or more carbon-carbon unsaturated bonds.

[0069] The inventors have discovered through research that the hydrophobic and oleophobic film layer of the specific embodiment of the present disclosure, formed by plasma chemical vapor deposition of monomer α of formula (1) and monomer β having two or more carbon-carbon unsaturated bonds, has excellent hydrophobic and oleophobic effects and hydrophobic and oleophobic stability. The plasma polymerization of monomer β and monomer α increases the crosslinking density of the polymer, thereby limiting the rearrangement of the perfluoropolyether chain and improving the hydrophobic stability.

[0070] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, the carbon-carbon unsaturated bond of the monomer β has a structure of formula (2):

[0071]

[0072] In formula (2), Z1, Z2 and Z3 are independently selected from hydrogen atom or C1-C4 alkyl group.

[0073] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, in formula (2), Z1 is selected from a hydrogen atom or a methyl group, and Z2 and Z3 are hydrogen atoms.

[0074] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, the monomer β has a structure of formula (3),

[0075]

[0076] In formula (3), R5, R6, R7, R8, R9 and R 10 R is independently selected from a hydrogen atom or a C1-C4 alkyl group; 11 C2-C 10 wherein the substituent of the substituted alkylene group is a C1-C4 alkyl group or a C1-C4 hydroxyalkyl group. x is an integer from 1 to 10.

[0077] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, in formula (3), R5, R6, R7, R8, R9 and R 10 In some embodiments, R6 and R8 are independently selected from hydrogen atoms or methyl groups, R5, R7, R9 and R 10 A hydrogen atom.

[0078] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, in formula (3), R5, R6, R7, R8, R9 and R 10 is a hydrogen atom, R 11 is ethylene, and x is 2.

[0079] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, in formula (3), R5, R6, R7, R8, R9 and R 10 is a hydrogen atom, R 11 is hexamethylene, and x is 1.

[0080] In the hydrophobic and oleophobic film layer of the specific embodiment of the present disclosure, in some specific embodiments, 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.

[0081] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, the monomer β has a structure of formula (4),

[0082]

[0083] In formula (4), R 12 C1-C 10 Alkyl, or C 1- C 10 The alkyl group, R 13 、R 14 and R 15 Each independently selected from C1-C 10 Alkylene, R 16 、R 17 and R 18 Each independently selected from C2-C 10 Alkylene, R 19 、R 20 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 and R 27 Each of y1, y2 and y3 is independently selected from a hydrogen atom or a C1-C4 alkyl group, and each of y1, y2 and y3 is independently selected from an integer from 0 to 10.

[0084] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, in formula (4), R 12 is a C1-C4 alkyl group or a C1-C4 hydroxyalkyl group, R 13 、R 14 and R 15 are independently selected from C1-C4 alkylene, R 16 、R 17 and R 18 are independently selected from C2-C4 alkylene, R 19 、R 20 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 and R 27 are independently selected from a hydrogen atom or a methyl group, and y1, y2 and y3 are independently selected from an integer from 0 to 2.

[0085] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, in formula (4), R 12 is ethyl, R 19 、R 20 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 and R 27 is a hydrogen atom, R 13 、R 14 and R 15 is a methyl group, and y1, y2 and y3 are 0.

[0086] In the hydrophobic and oleophobic film layer of the specific embodiment of the present disclosure, in some specific embodiments, the monomer β is selected from at least one of trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane triacrylate.

[0087] In the hydrophobic and oleophobic film layer of the specific embodiment of the present disclosure, in some specific embodiments, 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.

[0088] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, the monomer β is selected from one or more of diethylene glycol diacrylate, trimethylolpropane triacrylate, and 1,6-hexanediol diacrylate.

[0089] In the hydrophobic and oleophobic film layer of the present disclosure, the molar ratio of monomer α to monomer β is related to the hydrophobic and oleophobic properties, as well as the hydrophobic and oleophobic stability of the hydrophobic and oleophobic film layer. Therefore, the molar ratio of monomer α to monomer β can be set according to the requirements for water contact angle and oil contact angle in actual applications. In some embodiments, the molar ratio of monomer α to monomer β is 0.5:9.5 to 9.5:0.5, and can be, for example, 0.5:9.5, 3:7, 1:9, 5:5, 7:3, 9:1, or 9.5:0.5, etc.

[0090] In the hydrophobic and 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.

[0091] In the hydrophobic and oleophobic film layer according to the specific embodiments 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.

[0092] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, the monomer α has a structure of formula (1), wherein R1, R2, and R3 are independently selected from a methyl group or a hydrogen atom. In some embodiments, R1 is a methyl group, and R2 and R3 are hydrogen atoms.

[0093] In some embodiments of the hydrophobic and oleophobic film layer of the present disclosure, in order to ensure a better cross-linking density, the weight average molecular weight of the monomer α is greater than 1000, for example, 1000, 2000, 3000, 4000 or 5000, etc.

[0094] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, in formula (1), L1 is selected from: substituted or unsubstituted C1-C4 alkylene.

[0095] In the hydrophobic and oleophobic film layer of the present disclosure, in some embodiments, the substituted substituent is one or more of the following groups: alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclic, carboxyl, carboxylate, carboxylate, carbamate, alkoxy, ketone, aldehyde, amine, amide, hydroxyl, nitrile, nitrite, and halogen. In some embodiments, L1 is a linear or branched perfluoroalkylene group. In some embodiments, L1 is a perfluoroalkylene group.

[0096] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, the perfluoropolyether segment comprises a K-type structure, and the monomer α has a structure shown in formula (5).

[0097]

[0098] In formula (5), a is an integer not less than 1; L2 is selected from a linking 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 the following groups: an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a heterocyclic group, a carboxyl group, a carboxylate group, a carboxylate group, a carbamate group, an alkoxy group, a ketone group, an aldehyde group, an amine group, an amide group, a hydroxyl group, a nitrile group, a nitrite group, and a halogen.

[0099] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, the perfluoropolyether segment comprises a Y-shaped structure, and the monomer α has a structure shown in formula (6).

[0100]

[0101] In formula (6), b is an integer not less than 1, c is an integer not less than 1; L3 is selected from a linker, a substituted or unsubstituted C1-C3 alkylene group; and the substituted substituent is selected from one or more of the following groups: an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a heterocyclic group, a carboxyl group, a carboxylate group, a carboxylate group, a carbamate group, an alkoxy group, a ketone group, an aldehyde group, an amine group, an amide group, a hydroxyl group, a nitrile group, a nitrite group, and a halogen group.

[0102] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, the perfluoropolyether segment comprises a Z-type structure, and the monomer α has a structure shown in formula (7).

[0103]

[0104] In formula (7), d is an integer not less than 1, e is an integer not less than 1; L4 is a linking bond or a substituted or unsubstituted C1-C3 alkylene group; the substituted substituent is selected from one or more of the following groups: alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclic group, carboxyl, carboxylate, carboxylate, carbamate, alkoxy, ketone, aldehyde, amine, amide, hydroxyl, nitrile, nitrite, and halogen.

[0105] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, the perfluoropolyether segment comprises a D-type structure, and the monomer α has a structure shown in formula (8).

[0106]

[0107] In formula (8), f is an integer not less than 1; L5 is selected from a linking 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 the following groups: an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a heterocyclic group, a carboxyl group, a carboxylate group, a carboxylate group, a carbamate group, an alkoxy group, a ketone group, an aldehyde group, an amine group, an amide group, a hydroxyl group, a nitrile group, a nitrite group, and a halogen group.

[0108] In some embodiments of the hydrophobic and oleophobic film layer disclosed herein, in formulas (5) to (8), R1 is a methyl group.

[0109] In some specific embodiments of the hydrophobic and oleophobic film layer disclosed herein, the water contact angle of the hydrophobic and oleophobic film layer is greater than 95°, and the n-hexadecane contact angle of the hydrophobic and oleophobic film layer is greater than 60°.

[0110] In some specific embodiments of the hydrophobic and oleophobic film layer disclosed herein, the water contact angle of the hydrophobic and oleophobic film layer is greater than 108°, and the n-hexadecane contact angle of the hydrophobic and oleophobic film layer is greater than 65°.

[0111] Specific embodiments of the present disclosure further provide a device, wherein at least a portion of the surface of the device has any of the above hydrophobic and oleophobic films. In some specific embodiments, the entire surface of the device has the hydrophobic and oleophobic films, which is used to achieve a long-term and stable hydrophobic and oleophobic effect.

[0112] The device of the specific embodiment of the present disclosure, in some specific embodiments, includes an electrical component, an optical instrument, an electronic or electrical component, and the like.

[0113] The specific embodiment of the present disclosure also provides a method for preparing any of the above hydrophobic and oleophobic film layers, the preparation method comprising: placing a substrate in a plasma reaction chamber; vaporizing monomer α and monomer β and passing them into the plasma reaction chamber, starting plasma discharge, and chemically vapor depositing the plasma of monomer α and monomer β on the surface of the substrate to form the hydrophobic and oleophobic film layer.

[0114] In some specific embodiments of the preparation method disclosed herein, the steps of vaporizing monomer α and monomer β and then introducing them into the plasma reaction chamber include: dissolving monomer α, a fluorinated solvent, and a polymerization inhibitor in each other and then adding them into a monomer tank one, and adding monomer β into a monomer tank two; and heating the monomer tank one and the monomer tank two to vaporize monomer α and monomer β and then introducing them into the plasma reaction chamber respectively.

[0115] The preparation method of the specific embodiment of the present disclosure controls the molar amount of monomer α relative to monomer β entering the plasma reaction chamber during the coating time by controlling the flow ratio of monomer α and monomer β. The molar ratio of monomer α to monomer β is related to the hydrophobicity, oleophobicity, and hydrophobic and oleophobic stability of the hydrophobic and oleophobic film layer. 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 from the monomer tank 1 to the gas flow rate from the monomer tank 2 to the plasma reaction chamber is 0.5:9.5 to 9.5:0.5, and specifically can be: 0.5:9.5, 3:7, 1:9, 5:5, 7:3, 9:1, or 9.5:0.5, etc.

[0116] In the preparation method of the specific embodiment of the present disclosure, in some specific embodiments, the ratio of the gas flow rate from the first monomer tank to the plasma reaction chamber to the gas flow rate from the second monomer tank to the plasma reaction chamber is 3:7 to 9.5:0.5. In some specific embodiments, the ratio of the gas flow rate from the first monomer tank to the gas flow rate from the second monomer tank to the plasma reaction chamber is 5:5 to 9.5:0.5.

[0117] In the preparation method of the specific embodiment of the present disclosure, in some specific embodiments, the gas flow rate from the monomer tank to the plasma reaction chamber is 10 to 2000 μL / min, and specifically can be: 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, etc. In some specific embodiments, the gas flow rate from the monomer tank 2 into the plasma reaction chamber is 10 to 2000 μL / min, for example, it can be: 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, etc.

[0118] The preparation method of the specific embodiment of the present disclosure, since the molecular weight of monomer α is high and has a certain viscosity, a fluorine-containing solvent is added to ensure that the monomer is smoothly passed 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: 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 one or more of 3M electronic fluorinated liquid 7700.

[0119] In the preparation method of the specific embodiments of the present disclosure, in some specific embodiments, the weight ratio of the monomer α to the fluorine-containing solvent is 1:9 to 9:1, and specifically can be: 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, etc.

[0120] In the preparation method of the disclosed embodiments, a polymerization inhibitor is added to monomer α to prevent polymerization during the heating and vaporization process, thereby preventing polymerization and polymer formation in the monomer tank. In some embodiments, the polymerization inhibitor includes one or more of hydroquinone, p-benzoquinone, methylhydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, and 2,6-di-tert-butyl-p-cresol.

[0121] In the preparation method of the specific embodiment of the present disclosure, in some specific embodiments, the amount of the polymerization inhibitor is 0.1% to 1% by mass of the amount of the monomer α, and specifically can be: 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1%, etc.

[0122] In the preparation method of the specific embodiments of the present disclosure, to prevent polymerization of monomer β during the heating and gasification process, in some specific embodiments, a polymerization inhibitor is further added to the monomer tank 2. The amount of the polymerization inhibitor is 0.1% to 1% by weight of the amount of monomer β, and specifically, for example, can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1%, etc. In some specific embodiments, the polymerization inhibitor includes one or more of hydroquinone, p-benzoquinone, methylhydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, and 2,6-di-tert-butyl-p-cresol.

[0123] In some embodiments of the preparation method disclosed herein, the molecular weight of the monomer β is not large, and it is not easy to initiate polymerization reaction during the heating and gasification process, and no polymerization inhibitor needs to be added.

[0124] In the preparation method of the specific embodiment of the present disclosure, in some specific embodiments, during the plasma polymerization process, the temperature of the reaction chamber is 30°C to 60°C, for example, 30°C, 40°C, 50°C, 55°C or 60°C, etc.

[0125] In some embodiments of the preparation method disclosed herein, the plasma discharge is continuous discharge, with a discharge power of 10 to 300 W, such as 10 W, 50 W, 100 W, 200 W, or 300 W. The discharge time is 60 to 36,000 s, such as 60 s, 360 s, 1,200 s, 2,400 s, 3,600 s, 7,200 s, or 36,000 s.

[0126] In some embodiments of the preparation method of the specific embodiments of the present disclosure, the plasma discharge is a pulsed discharge with a discharge power of 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 cycle 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 s, specifically, for example, 200 s, 360 s, 1,200 s, 2,400 s, 3,600 s, 7,200 s, or 36,000 s.

[0127] In some specific embodiments of the preparation method of the specific embodiment of the present disclosure, before the chemical vapor deposition, the pressure is evacuated to 10-200 mTorr, and a mixture of one or more gases selected from He, Ar, and O2 is introduced, and plasma discharge is started to pre-treat the substrate.

[0128] In some embodiments of the preparation method of the present disclosure, during pretreatment, the plasma discharge is continuous discharge, with a discharge power of 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.

[0129] In the preparation method of the specific embodiment of the present disclosure, in some specific embodiments, during the pretreatment, the plasma discharge is a pulsed discharge, and the discharge power is 10 to 500 W, and specifically, for example, it can be: 10 W, 50 W, 100 W, 180 W, 200 W, 300 W or 500 W, etc. The pulse duty cycle is 0.1% to 80%, and specifically, for example, it can be: 0.1%, 1%, 10%, 25%, 35%, 50%, 60%, 70% or 80%, etc. The pulse frequency is 10 to 500 Hz, and specifically, for example, it can be: 10 Hz, 100 Hz, 200 Hz, 250 Hz, 300 Hz or 500 Hz, etc. The discharge time is 600 to 2400 s, and specifically, for example, it can be: 60 s, 360 s, 600 s, 1200 s, 1800 s or 2400 s, etc.

[0130] In the preparation method of the specific embodiments of the present disclosure, in some specific embodiments, during the pretreatment, the plasma discharge mode 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, microwave 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, bare electrode radio frequency glow discharge, etc. In some specific embodiments, the multi-electrode discharge includes: discharge using a floating electrode as the third electrode, etc.

[0131] In some embodiments of the preparation method of the present disclosure, the preparation method further includes post-processing, wherein the post-processing comprises: after the hydrophobic and oleophobic film layer is formed on the surface of the substrate, introducing clean compressed air or an inert gas to restore the plasma reaction chamber to normal pressure, opening the plasma reaction chamber, and removing the substrate. In some embodiments, the inert gas is introduced at a flow rate of 5 to 300 sccm.

[0132] The present invention is further described below with reference to specific examples.

[0133] Example

[0134] Test method description

[0135] Water contact angle of hydrophobic and oleophobic films: tested according to GB / T 30447-2013 standard.

[0136] Oil contact angle of the hydrophobic and oleophobic film layer: The contact angle between the film layer and n-hexadecane was tested using an SDC-100 standard contact angle meter.

[0137] Double 85 test: A substrate with a hydrophobic and oleophobic film layer formed on its surface is placed in an environment with a temperature of 85°C and a humidity of 85% RH. At different times, the water contact angle and oil contact angle of the hydrophobic and oleophobic film layer are tested to characterize the stability of the hydrophobic and oleophobic properties of the film layer.

[0138] Example 1

[0139] The Si wafer was placed on the substrate support of the plasma chamber. The chamber was evacuated to 150 mTorr and helium was introduced at a flow rate of 200 sccm. The chamber temperature was set to 55°C.

[0140] The chamber pressure was maintained at 150 mTorr, the helium flow rate was maintained at 200 sccm, and the plasma continuous discharge was started with a discharge power of 300 W for 600 s to pretreat the substrate;

[0141] Then, 3M-7200 fluorinated liquid, monofunctional perfluoropolyether (meth) acrylate (molecular weight Mw≈1000) (Suzhou Cangmu New Materials Co., Ltd.), and hydroquinone were prepared into a uniform solution at a weight ratio of 7:3:0.012 and added to monomer tank one; diethylene glycol diacrylate (DEGDA) and hydroquinone were dissolved in a weight ratio of 1:0.004 and added to monomer tank two; after the monomers in monomer tank one and monomer tank two were vaporized at a vaporization temperature of 110°C, the gas in monomer tank one was The plasma chamber is fed with a flow rate of 210 μL / min, and the gas from the second monomer tank is fed into the plasma chamber at a flow rate of 90 μL / min, i.e., the flow ratio is 7:3; the chamber pressure is maintained at 150 mTorr, the helium flow rate is maintained at 200 sccm, and the radio frequency plasma discharge is turned on. The radio frequency energy output mode is pulsed, and plasma chemical vapor deposition is performed on the substrate surface, wherein the pulse duty cycle is 50%, the pulse frequency is 300 Hz, the pulse discharge power is 250 W, and the reaction time is 3600 s;

[0142] After the coating is completed, the chamber is filled with compressed air to restore the pressure to normal. The coated substrate is taken out and its water contact angle and oil contact angle are tested. The test results are listed in Table 1 below. The substrate is then placed in a high temperature and high humidity environment for a double 85 test. The test results are shown in Table 1 below. Figure 1 .

[0143] Example 2

[0144] The Si wafer was placed on the substrate support of the plasma chamber. The chamber was evacuated to 150 mTorr and helium was introduced at a flow rate of 200 sccm. The chamber temperature was set to 55°C.

[0145] The chamber pressure was maintained at 150 mTorr, the helium flow rate was maintained at 200 sccm, and the plasma continuous discharge was started with a discharge power of 300 W for 600 s to pretreat the substrate;

[0146] Then, 3M-7200 fluorinated liquid, monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw≈1000) (Suzhou Cangmu New Materials Co., Ltd.), and hydroquinone were prepared into a uniform solution at a weight ratio of 7:3:0.012 and added to monomer tank one; trimethylolpropane triacrylate (TMPTA), diethylene glycol diacrylate (DEGDA), and hydroquinone were dissolved in a weight ratio of 5:5:0.1 and added to monomer tank two; the monomers in monomer tank one and monomer tank two were vaporized at a vaporization temperature of 110°C. , the gas from monomer tank one is introduced into the plasma chamber at a flow rate of 210 μL / min, and the gas from monomer tank two is introduced into the plasma chamber at a flow rate of 90 μL / min, that is, the flow ratio is 7:3; the chamber pressure is maintained at 150 mTorr, the helium flow rate is maintained at 200 sccm, the radio frequency plasma discharge is turned on, the radio frequency energy output mode is pulsed, and plasma chemical vapor deposition is performed on the surface of the substrate, wherein the pulse duty cycle is 50%, the pulse frequency is 300 Hz, the pulse discharge power is 250 W, and the reaction time is 3600 s;

[0147] After the coating is completed, the chamber is filled with compressed air to restore the pressure to normal. The coated substrate is taken out and its water contact angle and oil contact angle are tested. The test results are listed in Table 1 below. The substrate is then placed in a high temperature and high humidity environment for a double 85 test. The test results are shown in Table 1 below. Figure 1 .

[0148] Comparative Example 1

[0149] The Si wafer was placed on the substrate support of the plasma chamber. The chamber was evacuated to 150 mTorr and helium was introduced at a flow rate of 200 sccm. The chamber temperature was set to 55°C.

[0150] The chamber pressure was maintained at 150 mTorr, the helium flow rate was maintained at 200 sccm, and the plasma continuous discharge was started with a discharge power of 300 W for 600 s to pretreat the substrate;

[0151] Then, 3M-7200 fluorinated liquid, monofunctional perfluoropolyether (meth) acrylate (molecular weight Mw≈1000) (Suzhou Cangmu New Materials Co., Ltd.), and hydroquinone were prepared into a uniform solution in a weight ratio of 7:3:0.012 and added to monomer tank one; after the monomer in monomer tank one was vaporized at a vaporization temperature of 110°C, the gas in monomer tank one was introduced into the plasma chamber at a flow rate of 300 μL / min; the cavity pressure was maintained at 150 mTorr, the helium flow rate was maintained at 200 sccm, the radio frequency plasma discharge was turned on, the radio frequency energy output mode was pulsed, and plasma chemical vapor deposition was performed on the substrate surface, wherein the pulse duty cycle was 50%, the pulse frequency was 300 Hz, the pulse discharge power was 250 W, and the reaction time was 3600 s;

[0152] After the coating is completed, the chamber is filled with compressed air to restore the pressure to normal. The coated substrate is taken out and its water contact angle and oil contact angle are tested. The test results are listed in Table 1 below. The substrate is then placed in a high temperature and high humidity environment for a double 85 test. The test results are shown in Table 1 below. Figure 1 .

[0153] Example 3

[0154] The Si wafer was placed on the substrate support of the plasma chamber. The chamber was evacuated to 100 mTorr and helium was introduced at a flow rate of 150 sccm. The chamber temperature was set to 55°C.

[0155] The chamber pressure was maintained at 100 mTorr, the helium flow rate was maintained at 150 sccm, and the plasma continuous discharge was started with a discharge power of 400 W for 600 s to pretreat the substrate.

[0156] Then, 3M-7200 fluorinated liquid, monofunctional perfluoropolyether (meth) acrylate (molecular weight Mw≈1000) (Suzhou Cangmu New Materials Co., Ltd.), and p-hydroxyanisole were prepared into a uniform solution at a weight ratio of 7:3:0.015 and added to monomer tank one; 1,6-hexanediol diacrylate (HDDA) and p-hydroxyanisole were dissolved in a weight ratio of 1:0.005 and added to monomer tank two; after the monomers in monomer tank one and monomer tank two were gasified at a gasification temperature of 110°C, the gas in monomer tank one was The plasma chamber was introduced at a flow rate of 285 μL / min, and the gas from the monomer tank 2 was introduced into the plasma chamber at a flow rate of 15 μL / min, i.e., the flow ratio was 9.5:0.5; the chamber pressure was maintained at 100 mTorr, the helium flow rate was maintained at 150 sccm, and the radio frequency plasma discharge was turned on. The radio frequency energy output mode was pulsed, and plasma chemical vapor deposition was performed on the substrate surface, wherein the pulse duty cycle was 35%, the pulse frequency was 500 Hz, the pulse discharge power was 200 W, and the reaction time was 3600 s;

[0157] After the coating is completed, the chamber is filled with compressed air to restore the pressure to normal. The coated substrate is taken out and its water contact angle and oil contact angle are tested. The test results are listed in Table 1 below. The substrate is then placed in a high temperature and high humidity environment for a double 85 test. The test results are shown in Table 1 below. Figure 2 .

[0158] Example 4

[0159] The Si wafer was placed on the substrate support of the plasma chamber. The chamber was evacuated to 100 mTorr and helium was introduced at a flow rate of 150 sccm. The chamber temperature was set to 55°C.

[0160] The chamber pressure was maintained at 100 mTorr, the helium flow rate was maintained at 150 sccm, and the plasma continuous discharge was started with a discharge power of 400 W for 600 s to pretreat the substrate.

[0161] Then, 3M-7200 fluorinated liquid, monofunctional perfluoropolyether (meth) acrylate (molecular weight Mw≈1000) (Suzhou Cangmu New Materials Co., Ltd.), and p-hydroxyanisole were prepared into a uniform solution in a weight ratio of 7:3:0.015 and added to monomer tank one; 1,6-hexanediol diacrylate (HDDA) and p-hydroxyanisole were dissolved in a weight ratio of 1:0.005 and added to monomer tank two; after the monomers in monomer tank one and monomer tank two were gasified at a gasification temperature of 110°C, the monomers in monomer tank one were added to the monomer tank two. The gas was introduced into the plasma chamber at a flow rate of 270 μL / min, and the gas from the monomer tank 2 was introduced into the plasma chamber at a flow rate of 30 μL / min, i.e., the flow ratio was 9:1; the chamber pressure was maintained at 100 mTorr, the helium flow rate was maintained at 150 sccm, and the radio frequency plasma discharge was turned on. The radio frequency energy output mode was pulsed, and plasma chemical vapor deposition was performed on the substrate surface, wherein the pulse duty cycle was 35%, the pulse frequency was 500 Hz, the pulse discharge power was 200 W, and the reaction time was 3600 s;

[0162] After the coating is completed, the chamber is filled with compressed air to restore the pressure to normal. The coated substrate is taken out and its water contact angle and oil contact angle are tested. The test results are listed in Table 1 below. The substrate is then placed in a high temperature and high humidity environment for a double 85 test. The test results are shown in Table 1 below. Figure 2 .

[0163] Example 5

[0164] The Si wafer was placed on the substrate support of the plasma chamber. The chamber was evacuated to 100 mTorr and helium was introduced at a flow rate of 150 sccm. The chamber temperature was set to 55°C.

[0165] The chamber pressure was maintained at 100 mTorr, the helium flow rate was maintained at 150 sccm, and the plasma continuous discharge was started with a discharge power of 400 W for 600 s to pretreat the substrate.

[0166] Then, 3M-7200 fluorinated liquid, monofunctional perfluoropolyether (meth) acrylate (molecular weight Mw≈1000) (Suzhou Cangmu New Materials Co., Ltd.), and p-hydroxyanisole were prepared into a uniform solution in a weight ratio of 7:3:0.015 and added to monomer tank one; 1,6-hexanediol diacrylate (HDDA) and p-hydroxyanisole were dissolved in a weight ratio of 1:0.005 and added to monomer tank two; after the monomers in monomer tank one and monomer tank two were gasified at a gasification temperature of 110°C, the monomers in monomer tank one were added to the monomer tank two. The gas was introduced into the plasma chamber at a flow rate of 210 μL / min, and the gas from the monomer tank 2 was introduced into the plasma chamber at a flow rate of 90 μL / min, i.e., the flow ratio was 7:3; the chamber pressure was maintained at 100 mTorr, the helium flow rate was maintained at 150 sccm, and the radio frequency plasma discharge was turned on. The radio frequency energy output mode was pulsed, and plasma chemical vapor deposition was performed on the substrate surface, wherein the pulse duty cycle was 35%, the pulse frequency was 500 Hz, the pulse discharge power was 200 W, and the reaction time was 3600 s;

[0167] After the coating is completed, the chamber is filled with compressed air to restore the pressure to normal. The coated substrate is taken out and its water contact angle and oil contact angle are tested. The test results are listed in Table 1 below. The substrate is then placed in a high temperature and high humidity environment for a double 85 test. The test results are shown in Table 1 below. Figure 2 .

[0168] Example 6

[0169] The Si wafer was placed on the substrate support of the plasma chamber. The chamber was evacuated to 100 mTorr and helium was introduced at a flow rate of 150 sccm. The chamber temperature was set to 55°C.

[0170] The chamber pressure was maintained at 100 mTorr, the helium flow rate was maintained at 150 sccm, and the plasma continuous discharge was started with a discharge power of 400 W for 600 s to pretreat the substrate.

[0171] Then, 3M-7200 fluorinated liquid, monofunctional perfluoropolyether (meth) acrylate (molecular weight Mw≈1000) (Suzhou Cangmu New Materials Co., Ltd.), and p-hydroxyanisole were prepared into a uniform solution in a weight ratio of 7:3:0.015 and added to monomer tank one; 1,6-hexanediol diacrylate (HDDA) and p-hydroxyanisole were dissolved in a weight ratio of 1:0.005 and added to monomer tank two; after the monomers in monomer tank one and monomer tank two were gasified at a gasification temperature of 110°C, the gas in monomer tank one was The gas in the monomer tank 2 is introduced into the plasma chamber at a flow rate of 150 μL / min, and the gas in the monomer tank 2 is introduced into the plasma chamber at a flow rate of 150 μL / min, that is, the flow ratio is 5:5; the chamber pressure is maintained at 100 mTorr, the helium flow rate is maintained at 150 sccm, and the radio frequency plasma discharge is turned on. The radio frequency energy output mode is pulsed, and plasma chemical vapor deposition is performed on the surface of the substrate, wherein the pulse duty cycle is 35%, the pulse frequency is 500 Hz, the pulse discharge power is 200 W, and the reaction time is 3600 s;

[0172] After the coating is completed, the chamber is filled with compressed air to restore the pressure to normal. The coated substrate is taken out and its water contact angle and oil contact angle are tested. The test results are listed in Table 1 below. The substrate is then placed in a high temperature and high humidity environment for a double 85 test. The test results are shown in Table 1 below. Figure 2 .

[0173] Example 7

[0174] The Si wafer was placed on the substrate support of the plasma chamber. The chamber was evacuated to 100 mTorr and helium was introduced at a flow rate of 150 sccm. The chamber temperature was set to 55°C.

[0175] The chamber pressure was maintained at 100 mTorr, the helium flow rate was maintained at 150 sccm, and the plasma continuous discharge was started with a discharge power of 400 W for 600 s to pretreat the substrate.

[0176] Then, 3M-7200 fluorinated liquid, monofunctional perfluoropolyether (meth) acrylate (molecular weight Mw≈1000) (Suzhou Cangmu New Materials Co., Ltd.), and p-hydroxyanisole were prepared into a uniform solution in a weight ratio of 7:3:0.015 and added to monomer tank one; 1,6-hexanediol diacrylate (HDDA) and p-hydroxyanisole were dissolved in a weight ratio of 1:0.005 and added to monomer tank two; after the monomers in monomer tank one and monomer tank two were gasified at a gasification temperature of 110°C, the monomers in monomer tank one were added to the monomer tank two. The gas was introduced into the plasma chamber at a flow rate of 90 μL / min, and the gas from the monomer tank 2 was introduced into the plasma chamber at a flow rate of 210 μL / min, i.e., the flow ratio was 3:7; the chamber pressure was maintained at 100 mTorr, the helium flow rate was maintained at 150 sccm, and the radio frequency plasma discharge was turned on. The radio frequency energy output mode was pulsed, and plasma chemical vapor deposition was performed on the substrate surface, wherein the pulse duty cycle was 35%, the pulse frequency was 500 Hz, the pulse discharge power was 200 W, and the reaction time was 3600 s;

[0177] After the coating is completed, the chamber is filled with compressed air to restore the pressure to normal. The coated substrate is taken out and its water contact angle and oil contact angle are tested. The test results are listed in Table 1 below. The substrate is then placed in a high temperature and high humidity environment for a double 85 test. The test results are shown in Table 1 below. Figure 2 .

[0178] Table 1 Water contact angle and oil contact angle test results

[0179] Water contact angle / ° Oil (n-hexadecane) contact angle / ° Example 1 115 72 Example 2 116 73 Comparative Example 1 118 75 Example 3 118 75 Example 4 116 74 Example 5 114 70 Example 6 109 66 Example 7 97 60

[0180] According to the test results in Table 1, the water contact angle and the oil (n-hexadecane) contact angle of the hydrophobic and oleophobic films of Example 1, Example 2 and Comparative Example 1 are similar. Figure 1 The double 85 test result diagram of Example 1, Example 2 and Comparative Example 1 in the specific embodiment of the present disclosure is shown. Figure 1 It can be seen that the water contact angle of the film layer in Comparative Example 1 seriously decreased starting from the second day in the double 85 test; while the water contact angle of the film layers of Example 1 and Example 2 decreased slowly, and 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 the preparation process.

[0181] According to the test results in Table 1, in Examples 3 to 7, as the gas flow rate ratio of monomer tank one:gas flow rate of monomer tank two increases from 9.5:0.5, to 9:1, to 7:3, to 5:5, to 3:7, and as the ratio of the gas flow rate of monomer tank two to the gas flow rate of monomer tank one increases, the water contact angle and the oil contact angle of the membrane layer tend to decrease. Figure 2The double 85 test result diagram of Examples 3 to 7 in the specific implementation of the present disclosure is shown in FIG. Figure 2 It can be seen that as the ratio of the monomer amount in monomer tank one to the monomer amount in monomer tank two decreases, the hydrophobic performance of the prepared membrane layer decreases and the water contact angle decreases. At the same time, the water contact angle decreases slowly in the double 85 test, and the hydrophobic stability is relatively high.

[0182] The above description is merely an exemplary embodiment for illustrating the principles of the present disclosure and is not intended to limit the scope of protection of the present disclosure. Those skilled in the art may make various modifications and improvements without departing from the spirit and substance of the present disclosure, and such modifications and improvements are also within the scope of protection of the present disclosure.

Claims

1. A hydrophobic and oleophobic film layer, characterized in that: The hydrophobic and oleophobic film layer is a plasma polymerized coating formed by contacting a substrate with plasma of monomer α and monomer β, wherein the monomer α has a structure of formula (1), ； （1） In formula (1), R1, R2 and R3 are independently selected from C1-C4 hydrocarbon groups or hydrogen atoms; R4 is selected from C1-C4 perfluorinated alkyl groups or fluorine atoms; L1 is a linking group; m is an integer not less than 1; in the m repeating units, n of each repeating unit is independently selected from an integer not less than 1; The monomer β has two or more carbon-carbon unsaturated bonds.

2. The hydrophobic and oleophobic film layer according to claim 1, characterized in that: The carbon-carbon unsaturated bond of the monomer β has the structure of formula (2), ； （2） In formula (2), Z1, Z2 and Z3 are independently selected from hydrogen atom or C1-C4 alkyl group.

3. The hydrophobic and oleophobic film layer according to claim 2, characterized in that: The monomer β has a structure of formula (3), ； （3） In formula (3), R5, R6, R7, R8, R9 and R 10 R is independently selected from a hydrogen atom or a C1-C4 alkyl group; 11 C2-C 10 Alkylene or substituted alkylene, x is an integer from 1 to 10; The substituent of the substituted alkylene group is a C1-C4 alkyl group or a C1-C4 hydroxyalkyl group.

4. The hydrophobic and oleophobic film layer according to claim 3, characterized in that: R5, R6, R7, R8, R9 and R 10 are independently selected from a hydrogen atom or a methyl group.

5. The hydrophobic and oleophobic film layer according to claim 3, characterized in that: 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.

6. The hydrophobic and oleophobic film layer according to claim 2, characterized in that: The monomer β has a structure of formula (4), ； （4） In formula (4), R 12 C1-C 10 Alkyl, or C 1- C 10 The alkyl group, R 13 、R 14 and R 15 Each independently selected from C1-C 10 Alkylene, R 16 、R 17 and R 18 Each independently selected from C2-C 10 Alkylene, R 19 、R 20 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 and R 27 Each of y1, y2 and y3 is independently selected from a hydrogen atom or a C1-C4 alkyl group, and each of y1, y2 and y3 is independently selected from an integer from 0 to 10.

7. The hydrophobic and oleophobic film layer according to claim 6, characterized in that: In formula (4), the R 12 is a C1-C4 alkyl group or a C1-C4 hydroxyalkyl group, wherein R 13 、R 14 and R 15 Each independently selected from C1-C4 alkylene, said R 16 、R 17 and R 18 Each independently selected from C2-C4 alkylene, said R 19 、R 20 、R 21 、R 22 、R 23 、R 24 、R 25 、R 26 and R 27 are independently selected from a hydrogen atom or a methyl group, and y1, y2 and y3 are independently selected from an integer from 0 to 2.

8. The hydrophobic and oleophobic film layer according to claim 6, characterized in that: The monomer β is selected from at least one of trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane triacrylate.

9. The hydrophobic and oleophobic film layer according to claim 1, characterized in that: 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.

10. The hydrophobic and oleophobic film layer according to claim 1, characterized in that: The monomer β is selected from one or more of diethylene glycol diacrylate, trimethylolpropane triacrylate, and 1,6-hexanediol diacrylate.

11. 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. The hydrophobic and oleophobic film layer according to claim 1, characterized in that: In formula (1), R1, R2 and R3 are independently selected from methyl groups or hydrogen atoms.

14. The hydrophobic and oleophobic film layer according to claim 1, characterized in that: In formula (1), R1 is a methyl group, and R2 and R3 are hydrogen atoms.

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

16. The hydrophobic and oleophobic film layer according to claim 1, characterized in that: In formula (1), L1 is selected from: substituted or unsubstituted C1-C4 alkylene groups.

17. The hydrophobic and oleophobic film layer according to claim 16, characterized in that: The substituted substituents are one or more of the following groups: alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclic, carboxyl, carboxylate, carboxylate, carbamate, alkoxy, ketone, aldehyde, amine, amide, hydroxyl, nitrile, nitrite, and halogen.

18. The hydrophobic and oleophobic film layer according to claim 17, characterized in that: In formula (1), L1 is a perfluorinated substituted alkylene group.

19. The hydrophobic and oleophobic film layer according to claim 1, characterized in that: The monomer α has a structure shown in formula (5), ； （5） In formula (5), a is an integer not less than 1; L2 is selected from a connecting 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, characterized in that: The monomer α has a structure shown in formula (6), ； （6） In formula (6), b is an integer not less than 1, c is an integer not less than 1; and L3 is selected from a connecting bond, or a substituted or unsubstituted C1-C3 alkylene group.

21. The hydrophobic and oleophobic film layer according to claim 1, characterized in that: The monomer α has a structure shown in formula (7), ； （7） In formula (7), d is an integer not less than 1, e is an integer not less than 1; and L4 is a connecting bond, or a substituted or unsubstituted C1-C3 alkylene group.

22. The hydrophobic and oleophobic film layer according to claim 1, characterized in that: The monomer α has a structure shown in formula (8), ； （8） In formula (8), f is an integer not less than 1; L5 is selected from a linking bond, a substituted or unsubstituted methylene group, or a substituted or unsubstituted ethylene group.

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

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

25. A method for preparing a hydrophobic and oleophobic film according to any one of claims 1 to 24, characterized in that: include: placing a substrate in a plasma reaction chamber; The monomers α and β are gasified and introduced into the plasma reaction chamber, and plasma discharge is started. The plasma of the monomers α and β is chemically vapor deposited on the surface of the substrate to form the hydrophobic and oleophobic film layer.

26. The method for preparing a hydrophobic and oleophobic film layer according to claim 25, characterized in that: The step of gasifying monomer α and monomer β and introducing them into the plasma reaction chamber comprises: Monomer α, fluorinated solvent and polymerization inhibitor are dissolved in each other and added into monomer tank 1, and monomer β is added into monomer tank 2; The monomer tank 1 and the monomer tank 2 are heated to gasify the monomer α and the monomer β and then introduced into the plasma reaction chamber respectively.

27. The method for preparing a hydrophobic and oleophobic film layer according to claim 26, characterized in that: The gas flow rate from the monomer tank 1 to the plasma reaction chamber is 10-2000 μL / min, and the gas flow rate from the monomer tank 2 to the plasma reaction chamber is 10-2000 μL / min.

28. The method for preparing 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. The method for preparing a hydrophobic and oleophobic film layer according to claim 26, wherein: A polymerization inhibitor is also 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 preparing 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. The method for preparing a hydrophobic and oleophobic film layer according to claim 26, wherein: The fluorine-containing solvent is a fluorocarbon solvent, and the fluorocarbon solvent includes: methyl perfluorobutyl ether, ethyl perfluorobutyl ether, 3-methoxyperfluorohexane, perfluorobutyl ethylpropyl 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 one or more of 3M electronic fluorinated liquid 7700.

32. The method for preparing a hydrophobic and oleophobic film layer according to claim 26 or 29, characterized in that: The polymerization inhibitor includes one or more of hydroquinone, p-benzoquinone, methylhydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, and 2,6-di-tert-butyl-p-cresol.

33. The method for preparing a hydrophobic and oleophobic film layer according to claim 26, wherein: The plasma discharge is continuous discharge, the discharge power is 10-300W, and the discharge time is 60-36000s.

34. The method for preparing a hydrophobic and oleophobic film layer according to claim 26, wherein: The plasma discharge is a pulse discharge with a discharge power of 10-400 W, a pulse duty cycle of 0.1%-80%, a pulse frequency of 10-500 Hz, and a discharge time of 200-36000 s.

35. The method for preparing a hydrophobic and oleophobic film layer according to claim 26, wherein: Also includes: Before the chemical vapor deposition, the pressure is evacuated to 10-200 mTorr, and one or a mixture of He, Ar, and O2 is introduced, and plasma discharge is started to pre-treat the substrate.

36. The method for preparing a hydrophobic and oleophobic film layer according to any one of claims 25-31 and 33-35, characterized in that: The plasma discharge mode includes: electrodeless discharge, single-electrode discharge, double-electrode discharge or multi-electrode discharge.

37. A device, characterized in that At least a portion of the surface of the device has the hydrophobic and oleophobic film layer according to any one of claims 1 to 24.

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