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 producing the same, which is prepared by plasma-enhanced chemical vapor deposition from a perfluoropolyether monomer containing a (meth)acrylate group, and has good hydrophobic and oleophobic properties, is environmentally friendly, and does not cause biological contamination when applied.

Description

[Technical Field]

[0001] This application is This is a national phase application of the international application PCT / CN2023 / 129205 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 202211513302.X, 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 presence of oxygen between the fluorinated units in their backbone eliminates the environmental issues faced by long-chain alkyl fluorocarbon compounds. Furthermore, their surface energy can be as low as 10-14 mN / m. Therefore, film layers with excellent hydrophobic and oleophobic properties can be produced by modifying them based on perfluoropolyether segments. Summary of the Invention

[0006] A specific embodiment of the present disclosure provides a hydrophobic and oleophobic film layer that is a plasma polymerized coating formed by contacting a substrate with a plasma comprising a monomer of formula (1). JPEG2025537385000017.jpg2696(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, and L1 is a linking moiety; m is an integer of 1 or more, and of the m repeating units, n in each repeating unit is independently selected from integers of 1 or more.

[0007] In some specific embodiments, in formula (1), R1, R2, and R3 are each independently selected from a methyl group or a hydrogen atom.

[0008] In some specific embodiments, in formula (1), R1 is a methyl group, and R2 and R3 are hydrogen atoms.

[0009] In some specific embodiments, the weight average molecular weight of the monomer of formula (1) is 500 or greater.

[0010] In some specific embodiments, the weight average molecular weight of the monomer of formula (1) is 1000 or greater.

[0011] In some specific embodiments, in formula (1), L1 is selected from substituted or unsubstituted C1 to C4 alkylene groups.

[0012] In some specific embodiments, 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 ion, 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.

[0013] In some specific embodiments, in formula (1), L1 is a perfluoroalkylene group.

[0014] In some specific embodiments, the monomer of formula (1) has the structure shown in formula (2). JPEG2025537385000018.jpg26123(2) In formula (2), 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.

[0015] In some specific embodiments, the monomer of formula (1) has the structure shown in formula (3). JPEG2025537385000019.jpg22121(3) In formula (3), b is an integer of 1 or more, c is an integer of 1 or more, and L3 is selected from a bond and a substituted or unsubstituted C1 to C3 alkylene group.

[0016] In some specific embodiments, the monomer of formula (1) has the structure shown in formula (4). JPEG2025537385000020.jpg22114(4) In formula (4), 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.

[0017] In some specific embodiments, the monomer of formula (1) has the structure shown in formula (5). JPEG2025537385000021.jpg21117(5) In formula (5), 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.

[0018] In some specific embodiments, the hydrophobic and oleophobic film layer has a water contact angle of 110 o The hydrophobic and oleophobic film layer has a contact angle of 65°C with n-hexadecane. o That's all.

[0019] A specific embodiment of the present disclosure further provides a method for producing the hydrophobic and oleophobic film layer described above, the method comprising: placing a substrate in a plasma reaction chamber; and dissolving a monomer of formula (1), a fluorine-containing solvent and a polymerization inhibitor in one another and then adding the resulting solution to a monomer tank; vaporizing the monomer and then introducing the vaporized monomer into the plasma reaction chamber; initiating plasma discharge; and chemically vapor-depositing the monomer on the substrate surface to form the hydrophobic and oleophobic film layer.

[0020] In some specific embodiments, the weight ratio of the monomer to the fluorine-containing solvent is 1:9 to 9:1.

[0021] In some specific embodiments, 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 Fluid 7100, 3M Electronically Fluorinated Fluid 7200, 3M Electronically Fluorinated Fluid 7300, 3M Electronically Fluorinated Fluid 7500, and 3M Electronically Fluorinated Fluid 7700.

[0022] In some specific embodiments, the amount of the polymerization inhibitor used is 0.1% to 1% by mass of the amount of the monomer used.

[0023] In some specific embodiments, 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.

[0024] In some specific embodiments, the flow rate of the gas introduced into the plasma reaction chamber after the monomer is vaporized is 10 to 2000 μL / min.

[0025] In some specific embodiments, the plasma discharge is a continuous discharge, with a discharge power of 10 to 300 W and a discharge time of 60 to 36,000 s.

[0026] In some specific embodiments, 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 36,000 s.

[0027] In some specific embodiments, the manufacturing method further includes, 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 O, and initiating a plasma discharge.

[0028] In some specific embodiments, the plasma discharge method comprises electrodeless discharge, single electrode discharge, dual electrode discharge, or multi-electrode discharge.

[0029] 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.

[0030] Compared with the prior art, the technical solutions of the embodiments of the present disclosure have the following beneficial effects: A specific embodiment of the present disclosure provides a hydrophobic-oleophobic film layer prepared by plasma enhanced chemical vapor deposition from a perfluoropolyether monomer containing a (meth)acrylate group, and the hydrophobic-oleophobic film layer has a water contact angle of 110°C. o The hydrophobic and oleophobic film layer has a contact angle of 65°C with n-hexadecane. o That's all. DETAILED DESCRIPTION OF THE INVENTION

[0031] 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.

[0032] To achieve a hydrophobic-oleophobic effect on the surface of a substrate, device, etc., while avoiding environmental concerns, a specific embodiment of the present disclosure provides a hydrophobic-oleophobic film layer, which is a plasma polymerized coating formed by contacting a substrate with a plasma comprising a monomer of formula (1). JPEG2025537385000022.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 moiety, m is an integer of 1 or greater, and n in each of the m repeating units is independently selected from an integer of 1 or greater.

[0033] In the hydrophobic and oleophobic film layer of a specific embodiment of the present disclosure, the inventors have found through research that the hydrophobic and oleophobic film layer formed by plasma enhanced chemical vapor deposition using the monomer of formula (1) has excellent hydrophobic and oleophobic properties. The reason for this is believed to be that the monomer has a perfluoropolyether group at one end and an acrylate structure at the other end, and after plasma polymerization, the perfluoropolyether group becomes the side chain end, and the fluorocarbon groups (-CF2 and -CF3) are concentrated on the surface of the film layer, resulting in low surface energy of the film layer and therefore excellent hydrophobic and oleophobic properties.

[0034] In the hydrophobic and oleophobic film layer of the specific embodiment of the present disclosure, in some specific embodiments, in formula (1), R1, R2, and R3 are each independently selected from a methyl group or a hydrogen atom.

[0035] In the hydrophobic and oleophobic film layer of the specific embodiment of the present disclosure, in some specific embodiments, R1 is a methyl group, and R2 and R3 are hydrogen atoms.

[0036] In the hydrophobic-oleophobic film layer of the specific embodiment of the present disclosure, in some specific embodiments, the weight-average molecular weight of the monomer of formula (1) is 500 or more, specifically, for example, 500, 800, 1000, 2000, 3000, or 5000. In some specific embodiments, the weight-average molecular weight of the monomer of formula (1) is 1000 or more, specifically, for example, 1000, 2000, 3000, 4000, or 5000.

[0037] 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.

[0038] In the hydrophobic and oleophobic film layer of specific embodiments of the present disclosure, in some specific embodiments, when L1 has a substituent, 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 hydroxyl group, a nitrile group, a nitroso group, and a halogen. In some specific embodiments, L1 is a linear or branched perfluoroalkylene group. In some specific embodiments, L1 is a perfluoroalkylene group.

[0039] 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 of formula (1) has the structure shown in formula (2). JPEG2025537385000023.jpg26123(2) In formula (2), 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.

[0040] In the hydrophobic and oleophobic film layer of specific embodiments of the present disclosure, in some specific embodiments, the perfluoropolyether segment comprises a Y-shaped structure, and the monomer of formula (1) has a structure shown in formula (3). JPEG2025537385000024.jpg22122(3) In formula (3), 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.

[0041] In the hydrophobic and 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 of formula (1) has the structure shown in formula (4). JPEG2025537385000025.jpg22114(4) In formula (4), 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.

[0042] In the hydrophobic and 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 of formula (1) has the structure shown in formula (5). JPEG2025537385000026.jpg21117(5) In formula (5), f is an integer of 1 or greater, 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.

[0043] In some specific embodiments of the hydrophobic and oleophobic film layer of the present disclosure, in formulas (2) to (5), R1 is a methyl group.

[0044] 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 110 o The contact angle of the hydrophobic and oleophobic film layer with n-hexadecane was 65°C. o Greater than.

[0045] 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 120 o The hydrophobic and oleophobic film layer has a contact angle of 70°C or more with n-hexadecane. o That's all.

[0046] Specific embodiments of the present disclosure further provide a device, wherein at least a portion of the surface of the device has the hydrophobic-oleophobic film layer described above, and in some specific embodiments, the entire surface of the device has the hydrophobic-oleophobic film layer described above to achieve the hydrophobic-oleophobic effect.

[0047] 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.

[0048] A specific embodiment of the present disclosure further provides a method for manufacturing the above-mentioned hydrophobic and oleophobic film layer, the method comprising: placing a substrate in a plasma reaction chamber; and dissolving the monomer of formula (1), a fluorine-containing solvent and a polymerization inhibitor in one another, adding the resulting solution to a monomer tank; heating the monomer tank to vaporize the monomer, and then introducing the vaporized monomer into the plasma reaction chamber; initiating plasma discharge; and chemical vapor deposition of the monomer on the substrate surface to form the hydrophobic and oleophobic film layer.

[0049] In the manufacturing method of specific embodiments of the present disclosure, since the monomer of formula (1) 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.

[0050] In some specific embodiments of the manufacturing method of the specific embodiments of the present disclosure, the weight ratio of the monomer 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.

[0051] In the manufacturing method of specific embodiments of the present disclosure, a polymerization inhibitor is added to prevent the monomer of formula (1) from polymerizing to form a polymer in the monomer tank during the heating and 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.

[0052] In some specific embodiments of the manufacturing method of the specific embodiments of the present disclosure, the amount of the polymerization inhibitor used may be 0.1% to 1% by mass of the amount of the monomer 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%.

[0053] In the manufacturing methods of the specific embodiments of the present disclosure, in some specific embodiments, the flow rate of the gas introduced into the plasma reaction chamber after the monomer in the monomer tank is vaporized is 10 to 2000 μL / min, and specifically may be, for example, 10 μL / min, 100 μL / min, 120 μL / min, 150 μL / min, 180 μL / min, 500 μL / min, 1000 μL / min, 1500 μL / min, or 2000 μL / min.

[0054] 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, or 60°C.

[0055] 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.

[0056] In some specific embodiments of the manufacturing method of the specific embodiments of the present disclosure, the plasma discharge is pulsed, and the discharge power is 10 to 400 W, specifically, for example, 10 W, 50 W, 100 W, 180 W, 200 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 s, specifically, for example, 200 s, 360 s, 1,200 s, 2,400 s, 3,600 s, 7,200 s, or 36,000 s.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] In the manufacturing method of the 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, 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, 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.

[0061] The present invention will be further described below with reference to specific examples. [Example]

[0062] Test method description

[0063] Water contact angle of hydrophobic and oleophobic film layer: Tested according to GB / T 30447-2013 standard.

[0064] 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. Example 1

[0065] The Si sheet was placed on a substrate holder in a plasma chamber, the chamber was evacuated to 20 mTorr, helium gas was introduced at a flow rate of 100 sccm, and the chamber temperature was set to 50°C.

[0066] The chamber pressure was maintained at 20 mTorr, the helium gas flow rate was maintained at 100 sccm, continuous plasma discharge was initiated, and the substrate was pretreated with continuous discharge at a discharge power of 100 W for 600 s.

[0067] Next, a homogeneous solution of 3M-7200 fluorinated liquid, monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw ≒ 500) (SuZhou Chemwells Advanced Materials CO., LTD), and p-hydroxyanisole was prepared in a weight ratio of 5:5:0.025. The solution was vaporized at 90°C. The gas was then introduced into a plasma chamber at a flow rate of 150 μL / min, the chamber pressure was maintained at 20 mTorr, and the helium gas flow rate was maintained at 100 sccm. Radio frequency plasma discharge was initiated using pulsed radio frequency energy output. Plasma chemical vapor deposition was performed on the substrate surface with a pulse duty ratio of 50%, a pulse frequency of 250 Hz, a pulse discharge power of 180 W, and a reaction time of 3600 s.

[0068] After the coating was completed, compressed air was introduced to return the chamber to normal pressure, and the coated substrate was taken out and tested for its water contact angle and oil contact angle. The test results are shown in Table 1 below. Example 2

[0069] The Si sheet was placed on a substrate holder in a plasma chamber, the chamber was evacuated to 20 mTorr, helium gas was introduced at a flow rate of 100 sccm, and the chamber temperature was set to 50°C.

[0070] The chamber pressure was maintained at 20 mTorr, the helium gas flow rate was maintained at 100 sccm, continuous plasma discharge was initiated, and the substrate was pretreated with continuous discharge at a discharge power of 100 W for 600 s.

[0071] 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 5:5:0.025. The solution was vaporized at 110°C. The gas was then introduced into a plasma chamber at a flow rate of 150 μL / min, the chamber pressure was maintained at 20 mTorr, and the helium gas flow rate was maintained at 100 sccm. A radio frequency plasma discharge was initiated using pulsed radio frequency energy output. The pulse duty ratio was 50%, the pulse frequency was 250 Hz, the pulse discharge power was 180 W, and the reaction time was 3600 s.

[0072] After the coating was completed, compressed air was introduced to return the chamber to normal pressure, and the coated substrate was taken out and tested for its water contact angle and oil contact angle. The test results are shown in Table 1 below. Example 3

[0073] The Si sheet was placed on a substrate holder in a plasma chamber, the chamber was evacuated to 20 mTorr, helium gas was introduced at a flow rate of 100 sccm, and the chamber temperature was set to 50°C.

[0074] The chamber pressure was maintained at 20 mTorr, the helium gas flow rate was maintained at 100 sccm, continuous plasma discharge was initiated, and the substrate was pretreated with continuous discharge at a discharge power of 100 W for 600 s.

[0075] Next, a homogeneous solution of 3M-7200 fluorinated liquid, monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw ≒ 2000) (SuZhou Chemwells Advanced Materials CO., LTD), and p-hydroxyanisole was prepared in a weight ratio of 5:5:0.025. The solution was vaporized at 110°C. The gas was then introduced into a plasma chamber at a flow rate of 150 μL / min, the chamber pressure was maintained at 20 mTorr, and the helium gas flow rate was maintained at 100 sccm. A radio frequency plasma discharge was initiated using pulsed radio frequency energy output. The pulse duty ratio was 50%, the pulse frequency was 250 Hz, the pulse discharge power was 180 W, and the reaction time was 3600 s.

[0076] After the coating was completed, compressed air was introduced to return the chamber to normal pressure, and the coated substrate was taken out and tested for its water contact angle and oil contact angle. The test results are shown in Table 1 below. Comparative Example 1

[0077] The Si sheet was placed on a substrate holder in a plasma chamber, the chamber was evacuated to 20 mTorr, helium gas was introduced at a flow rate of 100 sccm, and the chamber temperature was set to 50°C.

[0078] The chamber pressure was maintained at 20 mTorr, the helium gas flow rate was maintained at 100 sccm, continuous plasma discharge was initiated, and the substrate was pretreated with continuous discharge at a discharge power of 100 W for 600 s.

[0079] Next, 3M-7200 fluorinated liquid, bifunctional perfluoropolyether (meth)acrylate (molecular weight Mw≒2000) (Solvay Fluorolink® MD700), and p-hydroxyanisole were mixed in a 5:5:0.025 weight ratio to form a homogeneous solution. The mixture was vaporized at 110°C, and the gas was introduced into a plasma chamber at a flow rate of 150 μL / min. The chamber pressure was maintained at 20 mTorr, and the helium gas flow rate was maintained at 100 sccm. Radio frequency plasma discharge was initiated, and the radio frequency energy output method was pulsed to induce plasma chemical vapor deposition on the surface of the substrate. The pulse duty ratio was 50%, the pulse frequency was 250 Hz, the pulse discharge power was 180 W, and the reaction time was 3600 s.

[0080] After the coating was completed, compressed air was introduced to return the chamber to normal pressure, and the coated substrate was taken out and tested for its water contact angle and oil contact angle. The test results are shown in Table 1 below. Example 4

[0081] The Si sheet was placed on a substrate holder in a plasma chamber, the chamber was evacuated to 20 mTorr, helium gas was introduced at a flow rate of 100 sccm, and the chamber temperature was set to 50°C.

[0082] The chamber pressure was maintained at 20 mTorr, the helium gas flow rate was maintained at 100 sccm, and continuous plasma discharge was initiated. The substrate was pretreated with continuous discharge at a discharge power of 120 W for 600 s.

[0083] Next, a homogeneous solution of 3M-7300 fluorinated liquid, monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw ≒ 500) (SuZhou Chemwells Advanced Materials CO., LTD), and 2,6-di-t-butyl-p-cresol was prepared in a weight ratio of 3:7:0.015. The solution was vaporized at 90°C. The gas was then introduced into a plasma chamber at a flow rate of 120 μL / min, the chamber pressure was maintained at 20 mTorr, and the helium gas flow rate was maintained at 100 sccm. Radio frequency plasma discharge was initiated using pulsed radio frequency energy output. Plasma chemical vapor deposition was performed on the substrate surface with a pulse duty ratio of 25%, a pulse frequency of 200 Hz, a pulse discharge power of 200 W, and a reaction time of 7200 s.

[0084] After the coating was completed, compressed air was introduced to return the chamber to normal pressure, and the coated substrate was taken out and tested for its water contact angle and oil contact angle. The test results are shown in Table 1 below. Example 5

[0085] The Si sheet was placed on a substrate holder in a plasma chamber, the chamber was evacuated to 20 mTorr, helium gas was introduced at a flow rate of 150 sccm, and the chamber temperature was set to 50°C.

[0086] The chamber pressure was maintained at 20 mTorr, the helium gas flow rate was maintained at 150 sccm, continuous plasma discharge was initiated, and the substrate was pretreated with continuous discharge at a discharge power of 120 W for 600 s.

[0087] Next, a homogeneous solution of 3M-7500 fluorinated liquid, monofunctional perfluoropolyether (meth)acrylate (molecular weight Mw ≒ 500) (SuZhou Chemwells Advanced Materials CO., LTD), and hydroquinone was prepared in a weight ratio of 7:3:0.042. The solution was vaporized at 90°C. The gas was then introduced into a plasma chamber at a flow rate of 180 μL / min, the chamber pressure was maintained at 20 mTorr, and the helium gas flow rate was maintained at 150 sccm. A radio frequency plasma discharge was initiated using pulsed radio frequency energy output. The pulse duty ratio was 35%, the pulse frequency was 100 Hz, the pulse discharge power was 300 W, and the reaction time was 3600 s.

[0088] After the coating was completed, compressed air was introduced to return the chamber to normal pressure, and the coated substrate was taken out and tested for its water contact angle and oil contact angle. The test results are shown in Table 1 below.

[0089] [Table 1] Test results for water contact angle and oil contact angle JPEG2025537385000027.jpg41147

[0090] According to the test results in Table 1, comparing Examples 1, 2, and 3, it can be seen that as the molecular weight of the monofunctional perfluoropolyether (meth)acrylate increases, both the water contact angle and the oil contact angle increase, indicating excellent hydrophobicity and oleophobicity.

[0091] According to the test results in Table 1, when Example 3 and Comparative Example 1 are compared, it can be seen that when the molecular weights are the same, the film layer made with the monofunctional perfluoropolyether (meth)acrylate monomer has higher water contact angles and oil contact angles than the film layer made with the difunctional perfluoropolyether (meth)acrylate monomer, and therefore exhibits better hydrophobicity and oleophobicity.

[0092] According to the test results in Table 1, in Examples 1, 4, and 5, different fluorocarbon solutions and polymerization inhibitors were used, but the same monomer was used. The film layers produced by controlling different plasma discharge parameters and monomer flow rates all had excellent hydrophobicity and oleophobicity.

[0093] 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. A hydrophobic and oleophobic film layer, characterized in that it is a plasma polymerized coating formed by contacting a substrate with a plasma containing a monomer of formula (1). （１） In formula (1), R 1 , R 2 , 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 the linking site; m is an integer of 1 or more, and of the m repeating units, n in each repeating unit is independently selected from integers of 1 or more.

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

3. 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.

4. The hydrophobic and oleophobic film layer according to claim 1 , wherein the weight average molecular weight of the monomer of formula (1) is 500 or more.

5. 5. The hydrophobic and oleophobic film layer according to claim 4, wherein the weight average molecular weight of the monomer of formula (1) is 1,000 or more.

6. 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:

7. 7. The hydrophobic and oleophobic film layer according to claim 6, 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 carboxy group, a carboxylate ion, 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.

8. In formula (1), L 1 The hydrophobic and oleophobic film layer according to claim 7, wherein is a perfluoroalkylene group.

9. 2. The hydrophobic and oleophobic film layer according to claim 1, wherein the monomer of formula (1) has a structure shown in formula (2). （２） In formula (2), 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.

10. 2. The hydrophobic and oleophobic film layer according to claim 1, wherein the monomer of formula (1) has a structure shown in formula (3). （３） In formula (3), 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:

11. 2. The hydrophobic and oleophobic film layer according to claim 1, wherein the monomer of formula (1) has a structure shown in formula (4). （４） In formula (4), 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:

12. 2. The hydrophobic and oleophobic film layer according to claim 1, wherein the monomer of formula (1) has a structure shown in formula (5). （５） In formula (5), 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.

13. The water contact angle of the hydrophobic and oleophobic film layer is 110 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 12, characterized in that:

14. A method for producing the hydrophobic and oleophobic film layer according to any one of claims 1 to 13, comprising: placing the substrate in a plasma reaction chamber; and the monomer of formula (1), the fluorine-containing solvent and the polymerization inhibitor are dissolved in each other and then added to a monomer tank; the monomer is vaporized and then introduced into the plasma reaction chamber; plasma discharge is initiated; and the monomer is chemically vapor deposited on the substrate surface to form the hydrophobic and oleophobic film layer; A method for producing a hydrophobic and oleophobic film layer, comprising:

15. The method for manufacturing a hydrophobic and oleophobic film layer according to claim 14, wherein the weight ratio of the monomer to the fluorine-containing solvent is 1:9 to 9:

1.

16. 15. The method for producing a hydrophobic and oleophobic film layer according to claim 14, 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.

17. The method for producing a hydrophobic and oleophobic film layer according to claim 14, wherein the amount of the polymerization inhibitor used is 0.1% to 1% by mass of the amount of the monomer used.

18. 15. The method for producing a hydrophobic and oleophobic film layer according to claim 14, 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.

19. The method for manufacturing a hydrophobic and oleophobic film layer according to claim 14, wherein the flow rate of the gas introduced into the plasma reaction chamber after the monomer is vaporized is 10 to 2000 μL / min.

20. The method for producing a hydrophobic and oleophobic film layer according to claim 14, 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.

21. The method for producing a hydrophobic and oleophobic film layer according to claim 14, 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.

22. 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.

23. The method for producing a hydrophobic and oleophobic film layer according to any one of claims 14 to 22, wherein the plasma discharge method includes electrodeless discharge, single-electrode discharge, double-electrode discharge, or multi-electrode discharge.

24. A device, characterized in that at least a part of its surface is provided with the hydrophobic and oleophobic film layer according to any one of claims 1 to 13.

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