A film layer and a method for manufacturing the same

Abstract

The detailed description of the present disclosure provides a film layer prepared by plasma chemical vapor deposition from a polysiloxane monomer with two terminal hydroxyl groups or alkoxy groups and a di- or more isocyanate monomer or a di- or more isocyanate polymer monomer, the film layer having good hydrophobicity and abrasion resistance.

Description

TECHNICAL FIELD

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

[0002] Polyurethane can be made into foam plastic, rubber, paint, adhesive, synthetic leather and other products, which is usually made by polyaddition of polyisocyanate and polyol, and has excellent properties such as good mechanical properties, wear resistance, oil resistance, cold resistance, tear resistance, chemical corrosion resistance, and radiation resistance. However, the molecular structure of polyurethane contains urethane groups -NH-COO-, which has the disadvantage of poor water resistance, greatly limiting the application of polyurethane.

[0003] Due to the unique structure of organic silicon combining organic and inorganic phases and its extremely low surface energy, it has hydrophobicity. Organic silicon can effectively improve the hydrophobicity of polyurethane. In the patent document CN113429620A "Hydrophobic polyurethane foam modified by organosilicon compound and preparation method thereof", isocyanate is reacted with hydroxyl group to form urethane group, and then organosilicon segment is introduced into the main chain of polyurethane, successfully preparing polyurethane foam, and improving the oil-water selectivity in the oil-water separation process. In the patent document CN102838719B "Highly hydrophobic organosilicon-polyurethane thermal insulation composite material and preparation method", hydroxyl-terminated, amino-terminated polysiloxane and silane coupling agent containing hydroxyl and amino are introduced into the main chain or side chain of polyurethane molecule, and a petroleum pipeline protection and thermal insulation material with hydrophobicity is prepared. However, the preparation process of the above materials requires the use of solvents or complex synthesis steps, and is not suitable for the preparation of film layers.

[0004] Therefore, a new method is needed to prepare a polyurethane film layer with hydrophobicity. SUMMARY

[0005] The specific embodiment of the present disclosure provides a film layer, which is a plasma polymerized coating layer formed by plasma of a substrate contacting monomer α and monomer β, the monomer α has a structure of formula (1),

[0006]

[0007] In formula (1), R1 and R2 are independently selected from hydrogen atom or C1-C8 alkyl group; R3 and R4 are independently selected from: a bond, C1-C8 alkylene, C1-C8 substituted alkylene, C1-C8 arylalkylene, C1-C8 substituted arylalkylene, C1-C8 alicyclic alkylene or C1-C8 substituted alicyclic alkylene. 10 20 10 20 10 20 ​​​​​substituted aliphatic group, C1-C4substituted alkyl group, C1-C4substituted aryl group, C1-C4substituted aromatic group, C1-C4substituted alicyclic group, or C1-C4substituted aliphatic group; n is an integer not less than 0; and β is a di- or higher isocyanate or a di- or higher isocyanate multimer. 10 each independently selected from the group consisting of C1-C4alkyl group, C1-C4substituted alkyl group, C1-C4substituted aryl group, C1-C4substituted aromatic group, C1-C4substituted alicyclic group, or C1-C4substituted aliphatic group. 10 each independently selected from the group consisting of C1-C4alkyl group, C1-C4substituted alkyl group, C1-C4substituted aryl group, C1-C4substituted aromatic group, C1-C4substituted alicyclic group, or C1-C4substituted aliphatic group. 20 each independently selected from the group consisting of C1-C4alkyl group, C1-C4substituted alkyl group, C1-C4substituted aryl group, C1-C4substituted aromatic group, C1-C4substituted alicyclic group, or C1-C4substituted aliphatic group. 10 each independently selected from the group consisting of C1-C4alkyl group, C1-C4substituted alkyl group, C1-C4substituted aryl group, C1-C4substituted aromatic group, C1-C4substituted alicyclic group, or C1-C4substituted aliphatic group. 20 each independently selected from the group consisting of C1-C4alkyl group, C1-C4substituted alkyl group, C1-C4substituted aryl group, C1-C4substituted aromatic group, C1-C4substituted alicyclic group, or C1-C4substituted aliphatic group. 10 each independently selected from the group consisting of C1-C4alkyl group, C1-C4substituted alkyl group, C1-C4substituted aryl group, C1-C4substituted aromatic group, C1-C4substituted alicyclic group, or C1-C4substituted aliphatic group. 20 each independently selected from the group consisting of C1-C4alkyl group, C1-C4substituted alkyl group, C1-C4substituted aryl group, C1-C4substituted aromatic group, C1-C4substituted alicyclic group, or C1-C4substituted aliphatic group. n is an integer not less than 0; and β is a di- or higher isocyanate or a di- or higher isocyanate multimer.

[0008] In some embodiments, the substituents of the substituted alkylene group, substituted arylalkylene group, substituted alicyclic alkylene group, substituted alkyl group, substituted aryl group, and substituted alicyclic group are selected from the group consisting of halogen, hydroxyl group, alicyclic group, aryl group, and C1-C4alkyl group.

[0009] In some embodiments, R1and R2are hydrogen atoms.

[0010] In some embodiments, R3and R4are a bond or C1-C4alkylene group, and R5, R6, R7, R8, R9, and R 10 each independently selected from the group consisting of C1-C4alkyl group.

[0011] In some embodiments, R3and R4are a bond, and R5, R6, R7, R8, R9, and R 10 each is a methyl group.

[0012] In some embodiments, the monomer α has a weight average molecular weight of 200 or more.

[0013] In some embodiments, the monomer α has a weight average molecular weight of 500 to 2000.

[0014] In some embodiments, the monomer β is a di-isocyanate, di-isocyanate multimer, tri-isocyanate, or tri-isocyanate multimer.

[0015] In some embodiments, the monomer β is selected from one or more of hexamethylene diisocyanate, o-tolylene diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, m-xylene alkyl diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, L-lysine triisocyanate, hexamethylene diisocyanate trimer, isophorone diisocyanate trimer, and toluene diisocyanate trimer.

[0016] In some embodiments, the water contact angle of the film layer is above 100°.

[0017] The embodiments of the present disclosure further provide a preparation method of any of the film layers, the preparation method comprising: placing a substrate in a plasma reaction chamber; introducing monomer α and monomer β into the plasma reaction chamber after vaporization, and starting plasma discharge, so that the plasma of the monomer α and the monomer β is chemically vapor deposited on the surface of the substrate to form the film layer.

[0018] In some embodiments, the flow rate of the monomer α introduced into the vaporization chamber is 10-2000 μL / min, the flow rate of the monomer β introduced into the vaporization chamber is 10-2000 μL / min, and the ratio of the flow rates of the monomer α and the monomer β is 1:9-9:1.

[0019] In some embodiments, the ratio of the flow rates of the monomer α and the monomer β is 2:1-5:1.

[0020] In some embodiments, the plasma discharge is pulse discharge, the discharge power is 10-400 W, the pulse duty cycle is 0.1%-100%, and the discharge time is 200-36000 s.

[0021] The embodiments of the present disclosure further provide a product, at least part of the surface of which is provided with any of the film layers described above.

[0022] The embodiments of the present disclosure further provide a preparation method of any of the film layers, the preparation method comprising: placing a substrate in a plasma reaction chamber; introducing monomer α and monomer β into the plasma reaction chamber after vaporization, and starting plasma discharge, so that the plasma of the monomer α and the monomer β is chemically vapor deposited on the surface of the substrate to form the film layer.

[0023] Compared with the prior art, the technical scheme of the embodiments of the present disclosure has the following beneficial effects:

[0024] The film layer provided by the embodiments of the present disclosure is prepared by plasma chemical vapor deposition of polysiloxane monomers with two or more isocyanate groups, and has a water contact angle of above 100° and good hydrophobicity.

[0025] Further, the water contact angle of the film layer is above 109°, and after being rubbed by a dust-free cloth for 1000 times under a pressure of 1N, the water contact angle of the film layer is above 107°, and the film layer has good rubbing resistance and stable hydrophobicity under rubbing conditions. EMBODIMENT

[0026] A detailed description of specific embodiments of the disclosure follows, which describes exemplary implementations only, and which is not to be construed as limiting the disclosure.

[0027] The inventors have found that a film layer formed by plasma chemical vapor deposition using a siloxane monomer having a hydroxyl group or an alkoxy group at both ends and a di- or more isocyanate monomer or a di- or more isocyanate multimer monomer has excellent hydrophobic properties and rubbing resistance.

[0028] A detailed description of specific embodiments of the disclosure provides a film layer that is a plasma polymerized coating layer formed by plasma of a substrate contacting a monomer a and a monomer β, the monomer a having a structure of formula (1),

[0029]

[0030] In formula (1), R1and R2are each independently selected from a hydrogen atom or a C1-C8alkyl group. R3and R4are each independently selected from: a bond, a C1-C 10 alkylene group, a C1-C 20 halogen-substituted alkylene group, a C1-C 10 hydroxyl-substituted alkylene group, a C1-C 20 arylene group, a C1-C 10 substituted arylene group, a C1-C 20 alicyclic group, or a C1-C 10 substituted alicyclic group. R5, R6, R7, R8, R9, and R 10 are each independently selected from: a C1-C 20 alkyl group, a C1-C 10 substituted alkyl group, a C1-C 20 aromatic group, a C1-C 10 substituted aromatic group, a C1-C 20 alicyclic group, or a C1-C 10 substituted alicyclic group. n is an integer not less than 0. The monomer β is a di- or more isocyanate or a di- or more isocyanate multimer.

[0031] In some embodiments of the film layer of the specific embodiments of the disclosure, R1and R2are selected from a hydrogen atom. In some embodiments, R1and R2are selected from a C1-C4alkyl group, specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, or an isobutyl group.

[0032] In some embodiments of the film layer of the specific embodiments of the disclosure, R3and R4are each independently selected from: a C1-C 10 alkylene group, a C1-C 10 halogen-substituted alkylene group, a C1-C 10 hydroxyl-substituted alkylene group, a C1-C 20Alicyclic substituted alkylene groups, C1-C 20 Aromatic substituted alkylene groups, and C1-C 20 C1-C4 alkyl-substituted alkylene groups.

[0033] In some specific implementations, R3 and R4 are independently selected from: C1-C 10 aromatic subunits, C1-C 10 Halogen-substituted aromatic subunits, C1-C 10 hydroxyl-substituted aromatic subunits, C1-C 20 Alicyclic-substituted aromatic subunits, C1-C 20 Aromatic group-substituted aromatic subunits, and C1-C 20 C1-C4 alkyl-substituted aromatic subunits.

[0034] In some specific implementations, R3 and R4 are independently selected from: C1-C 10 alicyclic subunits, C1-C 10 Halogen-substituted alicyclic subunits, C1-C 10 hydroxyl-substituted alicyclic subunits, C1-C 20 alicyclic subunits substituted with alicyclic groups, C1-C 20 Aromatic group-substituted alicyclic subunits, and C1-C 20 C1-C4 alkyl-substituted alicyclic subunits.

[0035] In some embodiments of the film layer of this disclosure, R3 and R4 are each independently selected from linking bonds or C1-C4 alkylene groups.

[0036] In some specific embodiments of the film layer of this disclosure, R5, R6, R7, R8, R9 and R 10 Selected independently from: C1-C 10 Alkyl, C1-C 10 Halogen-substituted alkyl groups, C1-C 10 hydroxyl-substituted alkyl, C1-C 20 Alicyclic substituted alkyl groups, C1-C 20 Aromatic substituted alkyl groups, and C1-C 20 C1-C4 alkyl-substituted alkyl groups.

[0037] In some specific implementations, R5, R6, R7, R8, R9 and R 10 Selected independently from: C1-C 10 Aromatic groups, C1-C 10 Halogen-substituted aromatic groups, C1-C 10 hydroxyl-substituted aromatic groups, C1-C20 Alicyclic substituted aromatic groups, C1-C 20 Aromatic groups substituted with aromatic groups, and C1-C 20 C1-C4 alkyl-substituted aromatic groups.

[0038] In some specific implementations, R5, R6, R7, R8, R9 and R 10 Selected independently from: C1-C 10 alicyclic group, C1-C 10 Halogen-substituted alicyclic groups, C1-C 10 hydroxyl-substituted alicyclic group, C1-C 20 Alicyclic groups substituted with alicyclic groups, C1-C 20 Aromatic group-substituted alicyclic group, and C1-C 20 C1-C4 alkyl-substituted alicyclic groups.

[0039] In some specific implementations, R5, R6, R7, R8, R9 and R 10 Alkyl groups selected independently from C1-C4.

[0040] In some specific embodiments, R1 and R2 are hydrogen atoms, R3 and R4 are connecting bonds, and R5, R6, R7, R8, R9 and R 10 They are methyl groups, respectively.

[0041] In some specific embodiments, R1 and R2 are C1-C4 alkyl groups, R3 and R4 are each independently selected from linking bonds or C1-C4 alkyl groups, and R5, R6, R7, R8, R9 and R 10 They are methyl groups, respectively.

[0042] In some embodiments of the film layer disclosed herein, the weight-average molecular weight of monomer α is 200 or higher. In other embodiments, to achieve better hydrophobicity, the weight-average molecular weight of monomer α is 500 to 2000.

[0043] In some embodiments of the film layer disclosed herein, the monomer β is a diisocyanate or a diisocyanate polymer. In other embodiments, to improve hydrophobicity and abrasion resistance, the monomer β is a ternary isocyanate or a ternary isocyanate polymer.

[0044] In some embodiments, the monomer β is an aliphatic diisocyanate, which can be, for example, hexamethylene diisocyanate, isophorone diisocyanate, and L-lysine triisocyanate, and the like. In some embodiments, the monomer β is an aliphatic diisocyanate trimer, which can be, for example, hexamethylene diisocyanate trimer, and isophorone diisocyanate trimer, and the like.

[0045] In some embodiments, the monomer β is an aromatic diisocyanate, which can be, for example, o-tolidene diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, m-xylene alkyl diisocyanate, xylylene diisocyanate, and naphthalene diisocyanate, and the like. In some embodiments, the monomer β is an aromatic triisocyanate, which can be, for example, triphenylmethane triisocyanate, and toluene diisocyanate trimer, and the like.

[0046] In some embodiments, the monomer β is selected from one or more of hexamethylene diisocyanate, o-tolidene diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, m-xylene alkyl diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, L-lysine triisocyanate, hexamethylene diisocyanate trimer, isophorone diisocyanate trimer, and toluene diisocyanate trimer.

[0047] In some embodiments, the film layer of the present disclosure has good hydrophobic property. In some embodiments, the water contact angle of the film layer is above 100°. Further, the water contact angle of the film layer is above 105°. Further, the water contact angle of the film layer is above 109°.

[0048] In some embodiments, the film layer of the present disclosure has good abrasion resistance. In some embodiments, the water contact angle of the film layer decreases by 6% or less after 1000 times of rubbing with a lint-free cloth under 1 N pressure. Further, the water contact angle of the film layer decreases by 2% or less after 1000 times of rubbing with a lint-free cloth under 1 N pressure.

[0049] In some embodiments, the product of the present disclosure includes an electrical component, an optical instrument, an electronic or electrical component, and the like.

[0050] In some embodiments, the product of the present disclosure includes an electrical component, an optical instrument, an electronic or electrical component, and the like.

[0051] The detailed description of the present disclosure also provides a preparation method of any of the above film layers, the preparation method comprising: placing a substrate in a plasma reaction chamber; introducing monomer a and monomer β into the plasma reaction chamber after being vaporized, and turning on plasma discharge, so that the plasma of the monomer a and the monomer β is chemically vapor deposited on the surface of the substrate to form the film layer.

[0052] The preparation method of the detailed description of the present disclosure, in some embodiments, introducing monomer a and monomer β into the plasma reaction chamber after being vaporized comprises: adding monomer a into monomer tank one and adding monomer β into monomer tank two; introducing monomer a and monomer β into the plasma reaction chamber after being vaporized, respectively.

[0053] The preparation method of the detailed description of the present disclosure controls the molar ratio of monomer a to monomer β entering the plasma reaction chamber within the film plating time by controlling the flow ratio of monomer a to monomer β, and the molar ratio of monomer a to monomer β relates to the hydrophobicity and abrasion resistance of the film layer. The flow of monomer a and monomer β can be set according to the actual application requirement of the film layer. In some embodiments, the flow ratio of monomer a to monomer β introduced into the vaporization chamber is 1:9-9:1, and specific examples can be 1:9, 2:9, 3:9, 6:9, 9:9, 4:1, 9:3, 5:2 or 9:1, etc.

[0054] The preparation method of the detailed description of the present disclosure, in some embodiments, the flow ratio of monomer a to monomer β introduced into the vaporization chamber is 2:1-5:1. In some embodiments, the flow ratio of monomer a to monomer β is 5:2-4:1.

[0055] In some embodiments of the preparation method of the specific embodiments of the present disclosure, the flow rate of the monomer α into the vaporization chamber is 10-2000 μL / min, and specifically 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, 200 μL / min, 250 μL / min, 300 μL / min, 500 μL / min, 1000 μL / min, 1500 μL / min, or 2000 μL / min, etc. In some embodiments of the preparation method of the specific embodiments of the present disclosure, the flow rate of the monomer β into the vaporization chamber is 10-2000 μL / min, and specifically for example, it can be 10 μL / min, 20 μL / min, 50 μL / min, 60 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.

[0056] In some embodiments of the preparation method of the specific embodiments of the present disclosure, the temperature of the reaction cavity during the plasma polymerization process is 30-60°C, and specifically for example, it can be 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, or 60°C, etc.

[0057] In some embodiments of the preparation method of the specific embodiments of the present disclosure, the plasma discharge is continuous discharge, and the discharge power is 10-300 W, and specifically for example, it can be 10 W, 50 W, 100 W, 200 W, or 300 W, etc. The discharge time is 60-36000 s, and specifically for example, it can be 60 s, 360 s, 1200 s, 2400 s, 3600 s, 7200 s, or 36000 s, etc.

[0058] In some embodiments of the preparation method of the specific embodiments of the present disclosure, the plasma discharge is pulse discharge, and the discharge power is 10-400 W, and specifically for example, it can be 10 W, 50 W, 100 W, 180 W, 220 W, 250 W, 300 W, or 400 W, etc. The pulse duty cycle is 0.1%-100%, and specifically for example, it can be 0.1%, 1%, 10%, 25%, 35%, 45%, 50%, 60%, 70%, or 80%, etc. The discharge time is 200-36000 s, and specifically for example, it can be 200 s, 360 s, 1200 s, 2400 s, 3600 s, 7200 s, or 36000 s, etc.

[0059] The preparation method of the embodiment of the present disclosure, in some embodiments, before the chemical vapor deposition, vacuumize to 10-200 mTorr, and introduce a mixed gas of one or more of the gases He, Ar, and O2, and pre-treat the substrate by starting plasma discharge.

[0060] The preparation method of the embodiment of the present disclosure, in some embodiments, in the pre-treatment, the plasma discharge is continuous discharge, and the discharge power is 50-600 W, and specifically for example can be 50 W, 100 W, 120 W, 200 W, 250 W, 300 W, 400 W, or 600 W, etc.

[0061] The preparation method of the embodiment of the present disclosure, in some embodiments, in the pre-treatment, the plasma discharge is pulse discharge, and the discharge power is 10-500 W, and specifically for example can be 10 W, 50 W, 100 W, 180 W, 200 W, 250 W, 300 W, or 500 W, etc. The pulse duty cycle is 0.1%-100%, and specifically for example can be 0.1%, 1%, 10%, 25%, 35%, 50%, 60%, 70%, or 80%, etc. The discharge time is 60-2400 s, and specifically for example can be 60 s, 200 s, 360 s, 600 s, 1200 s, 1800 s, or 2400 s, etc.

[0062] The preparation method of the embodiment of the present disclosure, in some embodiments, in the pre-treatment, the plasma discharge mode includes electrodeless discharge, single-electrode discharge, double-electrode discharge, or multi-electrode discharge. In some embodiments, the electrodeless discharge includes radio frequency inductive coupling discharge, microwave discharge, etc. In some embodiments, the single-electrode discharge includes corona discharge, plasma jet formed by single-electrode discharge, etc. In some embodiments, the double-electrode discharge includes dielectric barrier discharge, bare electrode radio frequency glow discharge, etc. In some embodiments, the multi-electrode discharge includes discharge using a floating electrode as a third electrode, etc.

[0063] The preparation method of the embodiment of the present disclosure, in some embodiments, the preparation method further includes post-treatment, and the post-treatment includes: after the preparation of the film layer on the surface of the substrate is completed, clean compressed air or inert gas is introduced, the plasma reaction chamber is restored to normal pressure, the plasma reaction chamber is opened, and the substrate is taken out. In some embodiments, the inert gas is introduced, and the flow rate of the inert gas is 5-300 sccm.

[0064] The application is further illustrated by specific examples below.

[0065] Example

[0066] Test method description

[0067] Water contact angle of the film layer: tested according to the standard GB / T 30447-2013.

[0068] Abrasion resistance test: performed on an abrasion tester, the friction material is a dust-free cloth, and the water contact angle before and after 1000 times of friction is tested under the conditions of a pressure of 1 N and a speed of 50 r / min.

[0069] Example 1

[0070] The Si sheet was placed on the substrate holder in the plasma chamber, the chamber was vacuumed to 100 mTorr, helium was introduced at a flow rate of 150 sccm, and the chamber temperature was 55°C; the chamber gas pressure was maintained at 100 mTorr, the helium flow rate was maintained at 150 sccm, the plasma continuous discharge was turned on, the discharge power was 250 W, the discharge was continued for 200 s, and the substrate was pretreated;

[0071] The monomer 1, polydimethylsiloxane with hydroxyl groups at both ends (molecular weight Mw≈500) (purchased from Anhui Aiyouta Silicone Co., Ltd.) was added to monomer tank 1, and the monomer 2, isophorone diisocyanate was added to monomer tank 2; wherein the flow rate of monomer 1 was 150 μL / min, the flow rate of monomer 2 was 60 μL / min, and after being gasified at a gasification temperature of 100°C, they were introduced into the plasma chamber;

[0072] The chamber gas pressure was maintained at 100 mTorr, the helium flow rate was maintained at 150 sccm, the radio frequency power was turned on for discharge, the energy output mode of the radio frequency was pulse, the plasma chemical vapor deposition was performed on the surface of the substrate, wherein the pulse duty cycle was 45%, the pulse discharge power was 220 W, and the reaction time was 3600 s;

[0073] After the coating was completed, compressed air was filled to restore the chamber to normal pressure, the coated substrate was taken out, and its water contact angle was tested, and the test results are listed in Table 1 below.

[0074] Example 2

[0075] The Si sheet was placed on the substrate holder in the plasma chamber, the chamber was vacuumed to 100 mTorr, helium was introduced at a flow rate of 150 sccm, and the chamber temperature was 55°C; the chamber gas pressure was maintained at 100 mTorr, the helium flow rate was maintained at 150 sccm, the plasma continuous discharge was turned on, the discharge power was 250 W, the discharge was continued for 200 s, and the substrate was pretreated;

[0076] Monomer 1, polydimethylsiloxane with two end hydroxyl groups (molecular weight Mw≈1000) (purchased from Anhui Aiyouta Silicone Co., Ltd.) was added into monomer tank 1, and monomer 2, isophorone diisocyanate was added into monomer tank 2; wherein the flow rate of monomer 1 was 150 μL / min, and the flow rate of monomer 2 was 60 μL / min, and both were introduced into the plasma chamber after being gasified at a gasification temperature of 100°C;

[0077] The cavity pressure was maintained at 100 mTorr, the helium flow rate was maintained at 150 sccm, the radio frequency power was turned on to discharge, the energy output mode of the radio frequency was pulse, plasma chemical vapor deposition was carried out on the surface of the substrate, wherein the pulse duty cycle was 45%, the pulse discharge power was 220 W, and the reaction time was 3600 s;

[0078] After the film coating was completed, compressed air was filled to restore the pressure in the chamber to normal pressure, the coated substrate was taken out, and its water contact angle was tested. The test results are listed in Table 1 below.

[0079] Example 3

[0080] The Si sheet was placed on the substrate placing support in the plasma chamber, the chamber was evacuated to 100 mTorr, helium was introduced at a flow rate of 150 sccm, and the cavity temperature was 55°C; the cavity pressure was maintained at 100 mTorr, the helium flow rate was maintained at 150 sccm, the plasma continuous discharge was turned on, the discharge power was 250 W, and the discharge was continued for 200 s to pretreat the substrate;

[0081] Monomer 1, polydimethylsiloxane with two end hydroxyl groups (molecular weight Mw≈1000) (purchased from Anhui Aiyouta Silicone Co., Ltd.) was added into monomer tank 1, and monomer 2, isophorone diisocyanate was added into monomer tank 2; wherein the flow rate of monomer 1 was 200 μL / min, and the flow rate of monomer 2 was 50 μL / min, and both were introduced into the plasma chamber after being gasified at a gasification temperature of 100°C;

[0082] The cavity pressure was maintained at 100 mTorr, the helium flow rate was maintained at 150 sccm, the radio frequency power was turned on to discharge, the energy output mode of the radio frequency was pulse, plasma chemical vapor deposition was carried out on the surface of the substrate, wherein the pulse duty cycle was 45%, the pulse discharge power was 220 W, and the reaction time was 3600 s;

[0083] After the film coating was completed, compressed air was filled to restore the pressure in the chamber to normal pressure, the coated substrate was taken out, and its water contact angle was tested. The test results are listed in Table 1 below; and wear resistance test was carried out, and the test results are listed in Table 2 below.

[0084] Example 4

[0085] Si pieces were placed on the substrate holder in the plasma chamber, the chamber was evacuated to 100 mTorr, helium was introduced at a flow rate of 150 seem, and the chamber temperature was 55°C; the chamber pressure was maintained at 100 mTorr, the helium flow rate was maintained at 150 seem, and the plasma was continuously discharged at a power of 250 W for 200 s to pretreat the substrate;

[0086] Monomer 1, polydimethylsiloxane with two hydroxyl ends (molecular weight Mw ~ 1000) (purchased from Anhui Aiyouta Silicone Co., Ltd.) was added to monomer tank 1, and monomer 2, isophorone diisocyanate trimer, was added to monomer tank 2; the flow rate of monomer 1 was 200 μL / min, the flow rate of monomer 2 was 50 μL / min, and both were vaporized at a vaporization temperature of 100°C and then introduced into the plasma chamber;

[0087] The chamber pressure was maintained at 100 mTorr, the helium flow rate was maintained at 150 seem, and the RF power was discharged, with the energy output mode of the RF being pulse, to perform plasma chemical vapor deposition on the surface of the substrate, with a pulse duty cycle of 45%, a pulse discharge power of 220 W, and a reaction time of 3600 s;

[0088] After the coating was completed, compressed air was introduced to restore the chamber to normal pressure, the coated substrate was removed, its water contact angle was tested, and the test results are shown in Table 1 below; and wear resistance tests were performed, and the test results are shown in Table 2 below.

[0089] Comparative Example 1

[0090] Si pieces were placed on the substrate holder in the plasma chamber, the chamber was evacuated to 100 mTorr, helium was introduced at a flow rate of 150 seem, and the chamber temperature was 55°C; the chamber pressure was maintained at 100 mTorr, the helium flow rate was maintained at 150 seem, and the plasma was continuously discharged at a power of 250 W for 200 s to pretreat the substrate;

[0091] Monomer 1, polydimethylsiloxane with two hydroxyl ends (molecular weight Mw ~ 1000) (purchased from Anhui Aiyouta Silicone Co., Ltd.) was added to monomer tank 1, and the flow rate of monomer 1 was 250 μL / min, and both were vaporized at a vaporization temperature of 100°C and then introduced into the plasma chamber;

[0092] The chamber pressure was maintained at 100 mTorr, the helium flow rate was maintained at 150 seem, and the RF power was discharged, with the energy output mode of the RF being pulse, to perform plasma chemical vapor deposition on the surface of the substrate, with a pulse duty cycle of 45%, a pulse discharge power of 220 W, and a reaction time of 3600 s;

[0093] After the coating is completed, compressed air is filled to restore the chamber to normal pressure, and the coated substrate is removed. The water contact angle of the coated substrate is tested, and the test results are shown in Table 1 below. The abrasion resistance test is also performed, and the test results are shown in Table 2 below.

[0094] Table 1 Water contact angle test results

[0095] Water contact angle / ° Example 1 102 Example 2 105 Example 3 107 Example 4 109 Comparative Example 1 104

[0096] Table 2 Abrasion resistance test results

[0097] Initial water contact angle / ° Water contact angle after rubbing 1000 times / ° Example 3 107 101 Example 4 109 107 Comparative Example 1 104 84

[0098] According to the test results in Table 1, the monomer of the polydimethylsiloxane with two terminal hydroxyl groups is used to prepare the film layer in Comparative Example 1, the monomer of the polydimethylsiloxane with two terminal hydroxyl groups and the diisocyanate are used to prepare the film layer in Example 3, and the monomer of the polydimethylsiloxane with two terminal hydroxyl groups and the triisocyanate are used to prepare the film layer in Example 4. As can be seen from Table 1, the water contact angles of the film layers in Comparative Example 1, Example 3 and Example 4 increase in turn, indicating that the diisocyanate and the triisocyanate can improve the hydrophobicity of the film layer. The triisocyanate improves the cross-linking density of the macromolecule of the film layer, and the film layer prepared by the triisocyanate has better hydrophobicity than the film layer prepared by the diisocyanate.

[0099] Compared with Example 1, the polydimethylsiloxane with two terminal hydroxyl groups in Example 2 has a larger molecular weight. As the molecular weight increases, the flexibility of the polydimethylsiloxane main chain increases, and the hydrophobic methyl groups are more easily enriched on the surface of the film layer, thereby increasing the water contact angle, i.e., improving the hydrophobicity.

[0100] Compared with Example 2, the flow rate of the polydimethylsiloxane with two terminal hydroxyl groups in Example 3 is larger, i.e., more polydimethylsiloxane with two terminal hydroxyl groups enters the reaction chamber to react at the same time, and the content of the polydimethylsiloxane segment with hydrophobicity in the film layer increases, thereby improving the hydrophobicity of the film layer.

[0101] According to the test results in Table 2, the abrasion resistance of the film layers in Comparative Example 1, Example 3 and Example 4 gradually improves. The water contact angle of the film layer in Example 4 decreases the least after the pressure friction of the dust-free cloth 1N for 1000 times, and the film layer has the best abrasion resistance. The water contact angle of the film layer in Comparative Example 1 decreases the most after the pressure friction of the dust-free cloth 1N for 1000 times, and the film layer has the worst abrasion resistance. The diisocyanate and the polydimethylsiloxane with two terminal hydroxyl groups can form linear molecular chains, and there is a certain entanglement between the molecular chains, which is beneficial to improving the abrasion resistance. The triisocyanate and the polydimethylsiloxane with two terminal hydroxyl groups can form a cross-linked structure, which further enhances the abrasion resistance of the film layer.

[0102] The above merely illustrates the exemplary embodiments for describing the principles of the present disclosure, and is not intended to limit the protection scope of the present disclosure. Various modifications and improvements can be made by those of ordinary skill in the art without departing from the spirit and principle of the present disclosure, and these modifications and improvements are also within the protection scope of the present disclosure.

Claims

1. A film layer, characterized by, The film layer is a plasma polymerized coating formed by exposing a substrate to a plasma of a monomer alpha and a monomer beta, the monomer alpha having a structure of formula (1), ， （1） In formula (1), R1 and R2 are hydrogen atoms; R3and R4are each independently selected from the group consisting of a direct bond, C1-C 10 alkylene, C1-C 20 substituted alkylene, C1-C 10 arylene, C1-C 20 substituted arylene, C1-C 10 alicyclic alkylene, or C1-C 20 substituted alicyclic alkylene; R5, R6, R7, R8, R9and R 10 respectively independently selected from: C1-C 10 alkyl, C1-C 20 substituted alkyl, C1-C 10 aromatic, C1-C 20 substituted aromatic, C1-C 10 alicyclic or C1-C 20 substituted alicyclic; n is an integer not less than 0; The monomer alpha has a weight average molecular weight of 200 or more; The monomer beta is a diisocyanate, a diisocyanate trimer, a triisocyanate, or a triisocyanate trimer; The water contact angle of the film layer is 105 o The water contact angle of the film layer is reduced by 6% or less after rubbing 1000 times at a pressure of 1 N using a lint-free cloth.

2. The film layer of claim 1, wherein, The substituents of the substituted alkylene, substituted arylalkylene, substituted alicyclic alkylene, substituted alkyl, substituted aryl, and substituted alicyclic group are selected from halogen, hydroxyl, alicyclic group, aryl group, or C1-C4 alkyl.

3. The film layer of claim 1, wherein, R3and R4are a bond or C1-C4alkylene, R5, R6, R7, R8, R9and R 10 each independently selected from C1-C4alkyl.

4. The film layer of claim 3, wherein, R3and R4are a bond, R5, R6, R7, R8, R9, and R 10 are each methyl.

5. The film layer of claim 1, wherein, The monomer alpha has a weight average molecular weight of 500-2000.

6. The film layer of claim 1, wherein, The monomer beta is selected from one or more of hexamethylene diisocyanate, o-tolidene diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, m-xylene alkyl diisocyanate, xylene alkyl diisocyanate, naphthalene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, L-lysine triisocyanate, hexamethylene diisocyanate trimer, isophorone diisocyanate trimer, and toluene diisocyanate trimer.

7. A method for producing the film layer according to any one of claims 1 to 6, characterized by, The method comprises: exposing a substrate to a plasma reaction chamber; gasifying the monomer alpha and the monomer beta and introducing them into the plasma reaction chamber, and starting a plasma discharge, wherein the plasma of the monomer alpha and the monomer beta chemically vapor deposits on the surface of the substrate to form the film layer.

8. The method for producing a film layer according to claim 7, characterized by, The flow rate of the monomer alpha introduced into the gasification chamber is 10-2000 μL / min, and the flow rate of the monomer beta introduced into the gasification chamber is 10-2000 μL / min, and the ratio of the flow rates of the monomer alpha and the monomer beta is 1:9-9:

1.

9. The method for producing a film layer according to claim 8, characterized by, The ratio of the flow rates of the monomer alpha and the monomer beta is 2:1-5:

1.

10. The method of claim 7, wherein the film layer is prepared by a method comprising: The plasma discharge is a pulse discharge, the discharge power is 10-400 W, the pulse duty cycle is 0.1%-100%, and the discharge time is 200-36000 s.

11. A product characterized by, At least part of the surface of the product has the film layer according to any one of claims 1-6.

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