CN117904607A - Organosilicon nano hydrophobic film layer and preparation method thereof - Google Patents

Organosilicon nano hydrophobic film layer and preparation method thereof Download PDF

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CN117904607A
CN117904607A CN202211246102.2A CN202211246102A CN117904607A CN 117904607 A CN117904607 A CN 117904607A CN 202211246102 A CN202211246102 A CN 202211246102A CN 117904607 A CN117904607 A CN 117904607A
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plasma
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宗坚
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Jiangsu Favored Nanotechnology Co Ltd
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Abstract

The specific embodiment of the invention provides an organosilicon nano-hydrophobic film layer and a preparation method thereof, wherein the organosilicon nano-hydrophobic film layer is formed by siloxane monomer plasma polymerization deposition, in the preparation process, gaseous siloxane monomer is introduced, a double electrode is started to discharge into a plasma reaction chamber, and the siloxane monomer is formed on the surface of a substrate by plasma chemical vapor deposition. The preparation method provided by the specific embodiment of the invention effectively solves the problem that the difference of the film thickness of different positions on the surface of the substrate caused by the deposition of siloxane monomers in the plasma chamber is large, and is beneficial to improving the film coating speed and the wear resistance of the film.

Description

Organosilicon nano hydrophobic film layer and preparation method thereof
Technical Field
The invention belongs to the field of chemical protective coatings, and particularly relates to an organosilicon nano hydrophobic film layer and a preparation method thereof.
Background
The water contact angle of the surface of the material is generally required to be larger than 90 degrees, and the hydrophobic materials widely used at present are classified into siloxane materials and fluorine-containing materials, wherein the fluorine-containing materials are widely applied due to the excellent water and oil repellency. On a smooth surface, the fluorine-containing material can prepare a hydrophobic film layer with the highest water contact angle of about 120 degrees, however, the fluorine-containing material has the defects of poor friction resistance, high price, high temperature resistance, difficult degradation, carcinogenicity, reproductive toxicity, developmental toxicity, neurotoxicity and the like, so that the application of the fluorine-containing material is limited. The european union POPs regulations require banning the use of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) and derivatives thereof, and the united states packaging act TPCH requires perfluoroalkyl and polyfluoroalkyl species (PFAS) to be undetectable. Therefore, siloxane materials are the first choice for replacing fluorine-containing materials, and the study of silane hydrophobic materials is increasingly emphasized.
The method is suitable for various substrates, the deposited polymer protective coating is uniform, the coating preparation temperature is low, the coating thickness is thin, the stress is small, almost no damage is caused to the substrate surface and almost no influence is caused to the substrate performance, the siloxane monomer gas is formed into a hydrophobic protective film layer on the surface of the substrate by adopting a plasma deposition mode in related researches, but when the conventional common plasma process is adopted for coating, the difference of the coating thickness at different positions on the substrate surface is large when the siloxane monomer gas is adopted for coating, and the overall protective performance of the coating can be influenced.
Disclosure of Invention
The specific embodiment of the invention provides an organosilicon nano hydrophobic film layer and a preparation method thereof, and the specific scheme is as follows:
the preparation method of the organosilicon nano hydrophobic film layer comprises the following steps:
Placing a substrate in a plasma reaction chamber, wherein a double electrode suitable for discharging is arranged in the plasma reaction chamber, and the double electrode comprises: a center electrode arranged at the center of the plasma reaction chamber and a cavity wall electrode arranged on the inner wall of the plasma reaction chamber;
Introducing gaseous siloxane monomers into the plasma reaction chamber through the monomer air inlet, starting the double electrodes to discharge plasma in the plasma reaction chamber, and forming the organosilicon nano hydrophobic film layer on the surface of the substrate through plasma chemical vapor deposition of the siloxane monomers;
the siloxane monomer comprises at least one structure shown in the following formula (1) or (2),
In the formula (1) or (2), R 1、R2、R3、R5 and R 6 are respectively and independently selected from a hydrogen atom, halogen, substituted or unsubstituted alkyl of C 1-C12, substituted or unsubstituted alkoxy of C 1-C12 or substituted or unsubstituted alkyl siloxy of C 1-C12, at least one of R 1、R2 and R 3 is not a hydrogen atom, at least one of R 5 or R 6 is not a hydrogen atom, R 4 is substituted or unsubstituted alkyl of C 1-C12 or substituted or unsubstituted alkyl silicon of C 1-C12, n is an integer of 1-100, and m is an integer of 3-10.
Optionally, the central electrode comprises at least one cylindrical electrode, and the cavity wall electrode comprises at least one electrode plate.
Optionally, the central electrode and the cavity wall electrode are electrically connected to the same power supply.
Optionally, the plasma discharge is pulse discharge, the pulse duty ratio is 0.1% -80%, the pulse frequency is 10-500 Hz, the discharge power is 10-400W, and the discharge time is 200-36000 s.
Optionally, the preparation method of the organosilicon nano hydrophobic film layer further comprises the following steps: and a gauze is arranged between the monomer air inlet and the substrate, and the gaseous siloxane monomer passes through the gauze and then is subjected to plasma chemical vapor deposition on the surface of the substrate to form the organosilicon nano hydrophobic film layer.
Optionally, the mesh size of the gauze is 10-100 meshes.
Optionally, the flow rate of the siloxane monomer is 10-2000 mu L/min.
Optionally, a support is disposed in the plasma reaction chamber, a support member is disposed on the support member, and the substrate is disposed on the support member, and is driven to rotate in the reaction chamber by the rotation of the support member around a central axis of the support member and the rotation of the support member around the central axis of the support member.
Optionally, the rotating speed of the bracket is 1-10 rpm, and the rotating speed of the support piece is 1-10 rpm.
Optionally, the water contact angle of the organosilicon nano-hydrophobic film layer is not less than 105 degrees.
Optionally, the preparation method of the organosilicon nano hydrophobic film layer further comprises the following steps: before the chemical vapor deposition, vacuumizing to 10-200 millitorr, introducing one or more mixed gases of He, ar and O 2, and starting plasma discharge to pretreat the substrate.
Optionally, R 1、R2、R3、R5 and R 6 are each independently selected from methyl or ethyl, R 4 is methyl, ethyl or trimethylsilyl, and n is an integer from 2 to 10.
Alternatively, the siloxane monomers include a first siloxane monomer having one unsaturated double bond and a second siloxane monomer having at least two unsaturated double bonds.
Alternatively, the siloxane monomer I has a structure shown in the following formula (3),
,R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17 And R 18 in the formula (3) are respectively and independently selected from hydrogen atoms or C 1-C4 hydrocarbon groups, at least one of R 10、R11 and R 12 is not hydrogen atoms, at least one of R 13、R14 and R 15 is not hydrogen atoms, at least one of R 16、R17 and R 18 is not hydrogen atoms, and p is an integer of 1-10.
Optionally, R 7、R8 and R 9 are each independently selected from a hydrogen atom or a methyl group, and R 10、R11、R12、R13、R14、R15、R16、R17 and R 18 are each independently selected from a methyl group or an ethyl group.
Alternatively, the siloxane monomer one is methacryloxypropyl tris (trimethylsiloxy) silane.
Alternatively, the siloxane monomer II has a structure shown in a formula (2), R 5 is an olefin group of C 1-C4, and R 6 is an alkane group of C 1-C4.
Alternatively, the siloxane monomer II is 1,3,5, 7-tetravinyl-1, 3,5, 7-tetramethyl cyclotetrasiloxane.
The specific embodiment of the invention also provides an organosilicon nano-hydrophobic membrane layer, which is prepared by the preparation method of the organosilicon nano-hydrophobic membrane layer.
The specific embodiment of the invention also provides a device, wherein at least part of the surface of the device is provided with the organic silicon nanometer hydrophobic film layer.
According to the organic silicon nanometer hydrophobic film layer and the preparation method thereof, the organic silicon nanometer hydrophobic film layer is formed by siloxane monomer plasma polymerization deposition, in the preparation process, through arranging a central electrode and a cavity wall electrode which are suitable for discharging in a plasma reaction chamber, the central electrode and the cavity wall electrode are started to discharge to the plasma reaction chamber, so that the whole plasma reaction chamber is in an electric field uniformly distributed, the gaseous siloxane monomer is activated into plasma and uniformly deposited on the surface of a substrate, the problem that the difference of coating thicknesses of different positions of the surface of the substrate caused by the fact that the gaseous siloxane monomer directly enters the plasma chamber is large is effectively solved, and meanwhile, the wear resistance and the film forming speed of the prepared organic silicon nanometer hydrophobic film layer are improved, and meanwhile, the film quality and the film forming efficiency are improved.
Drawings
Fig. 1 shows a schematic structure of a coating apparatus used in a preparation method according to an embodiment of the present invention.
Detailed Description
The inventor of the present invention found in the study that when gaseous siloxane monomers directly enter a plasma chamber to be excited by plasma to polymerize and deposit on a substrate to form a film layer, the difference of coating thicknesses at different positions on the surface of the substrate may be relatively large due to the slow diffusion of the gaseous siloxane monomers, and by arranging double electrodes suitable for discharging in a plasma reaction chamber and rotating the substrate in the reaction chamber, the siloxane monomers can be uniformly distributed at different positions on the surface of the substrate, so as to effectively reduce the difference of coating thicknesses, so that the present invention provides a preparation method of an organosilicon nano hydrophobic film layer, comprising the following steps:
Placing a substrate in a plasma reaction chamber, wherein a double electrode suitable for discharging is arranged in the plasma reaction chamber, and the double electrode comprises: a center electrode arranged at the center of the plasma reaction chamber and a cavity wall electrode arranged on the inner wall of the plasma reaction chamber;
And introducing gaseous siloxane monomers into the plasma reaction chamber through the monomer air inlet, starting the double electrodes to discharge plasma in the plasma reaction chamber, and forming the organosilicon nano hydrophobic film layer on the surface of the substrate through plasma chemical vapor deposition of the gaseous siloxane monomers.
The preparation method of the organic silicon nanometer hydrophobic film layer in the specific embodiment of the invention, the siloxane monomer comprises at least one structure shown in the following formula (1) or (2),
In the formula (1) or (2), R 1、R2、R3、R5 and R 6 are respectively and independently selected from a hydrogen atom, halogen, substituted or unsubstituted alkyl of C 1-C12, substituted or unsubstituted alkoxy of C 1-C12 or substituted or unsubstituted alkyl siloxy of C 1-C12, at least one of R 1、R2 and R 3 is not a hydrogen atom, at least one of R 5 or R 6 is not a hydrogen atom, R 4 is substituted or unsubstituted alkyl of C 1-C12 or substituted or unsubstituted alkyl silicon of C 1-C12, n is an integer of 1-100, and m is an integer of 3-10. In a specific embodiment of the present invention, the hydrocarbon group may be an alkane group, alkene group, alkyne group or arene group, and the substituent may be, for example, a halogen atom, hydroxyl group, acyloxy group, amine group, nitrile group or hydrocarbyloxy group, etc., as specific examples, the siloxane monomer can be diphenyl dimethoxy silane, methyl orthosilicate, ethyl orthosilicate, diethyl amino methyl triethoxy silane, diethylenetriamine propyl trimethoxy silane, 1-trimethyl-N-2-propylene propylamine silane, bis [3- (trimethoxysilyl) propyl ] ethylenediamine, pentamethyldisiloxane, hexamethyldisiloxane, hexamethoxydisiloxane, hexaphenyldisiloxane, vinylpentamethyldisiloxane, 1-vinyl-1133-tetramethyldisiloxane, 1, 3-octyltetramethyldisiloxane, 1, 3-tetramethyl-1, 3-diphenyldisiloxane pentamethyldisiloxane, hexamethyldisiloxane, hexamethoxydisiloxane, hexaphenyldisiloxane, vinyl pentamethyldisiloxane 1-vinyl-1133-tetramethyldisiloxane, 1, 3-octyltetramethyldisiloxane, 1, 3-tetramethyl-1, 3-diphenyldisiloxane, 3- [ [ dimethyl (vinyl) silyl ] oxy ] -1, 5-tetramethyl-3-phenyl-1, 5-divinyl trisiloxane, 1, 5-dichloro-1, 3, 5-hexamethyltrisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, 1,3,5, 7-octamethyltetrasiloxane, 1, 7-dichloro-1, 3,5, 7-octamethyltetrasiloxane dodecyl methyl pentasiloxane, decamethyl dihydro pentasiloxane, tetradecyl methyl hexasiloxane, 1,1,3,3,5,5,7,7,9,9,11,11-dodecyl methyl hexasiloxane, hexadecyl heptasiloxane, 1,1,3,3,5,5,7,7,9,9,11,11,13,13-tetradecyl methyl heptasiloxane, 1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15-hexadecyl methyl octasiloxane, polydimethyl siloxane, polymethylhydrosiloxane, polydimethyl siloxane hydride end-caps polyphenyl methylsiloxanes, vinyl-terminated dimethylpolysiloxanes, phenyltris (trimethylsiloxy) silanes, vinyltris (trimethylsiloxy) silanes, methyltri (trimethylsiloxy) silanes, ethyltris (trimethylsiloxy) silanes, 1,1,1,3,5,7,7,7-octamethyl-3, 5-bis (trimethylsiloxy) tetrasiloxane, 1, 3-diphenyl-1, 3-bis (trimethylsiloxy) disiloxane, allyltris (trimethylsiloxy) silanes, tetrakis (trimethylsiloxy) silanes, (3-chloropropyl) tris (trimethylsiloxy) silanes, methacryloxypropyl tris (trimethylsiloxy) silanes, hexamethylcyclotrisiloxane, hexaethylcyclotrisiloxane, hexaphenyl cyclotrisiloxane, hexaethyl cyclotrisiloxane, 2,4, 6-triethyl-2, 4, 6-trimethyl cyclotrisiloxane, 1,3, 5-trivinyl-1, 3, 5-trimethyl cyclotrisiloxane, 2,4, 6-trimethyl cyclotrisiloxane, trimethyl-1, 3, 5-triphenyl cyclotrisiloxane, 2,4, 6-trivinyl-2, 4, 6-trimethyl cyclotrisiloxane, octamethyl cyclotrisiloxane, octaphenyl cyclotrisiloxane, 2, 4-tetramethyl-6,6,8,8-tetraphenyl cyclotrisiloxane, decamethyl cyclopentasiloxane, 2,4,6, 8-tetramethyl-2, 4,6, 8-tetravinyl cyclotrisiloxane 1,3,5, 7-tetravinyl-1, 3,5, 7-tetramethyl cyclotetrasiloxane, 2,4,6, 8-tetramethyl-2- [3- (oxiranylmethoxy) propyl ] cyclotetrasiloxane, 2, 4-divinyl-2,4,6,6,8,8-hexamethylcyclotetrasiloxane, pentamethyl pentavinyl cyclopentasiloxane, 2,4,6,8, 10-pentamethyl cyclopentasiloxane, dodecyl cyclohexa-vinyl cyclotrisiloxane, hexadecyl-Xin Guiyang-siloxane, or octadecyl-cyclononane, and the like.
In some embodiments, the abrasion resistance and the hydrophobicity are both considered, the R 1、R2、R3、R5 and the R 6 are respectively and independently selected from methyl or ethyl, especially methyl, the R 4 is methyl, ethyl or trimethylsilyl, especially methyl or trimethylsilyl, the n is an integer of 2-10, and the siloxane monomer can be hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecyltetrasiloxane, hexamethylcyclotrisiloxane, hexaethylcyclotrisiloxane, octamethyltetrasiloxane, octaethylcyclotetrasiloxane, decamethylpentasiloxane or dodecamethylcyclotrisiloxane, etc.
In some embodiments, the silicone monomers include a first silicone monomer having one unsaturated double bond and a second silicone monomer having at least two unsaturated double bonds, in view of better abrasion resistance of the silicone nano-hydrophobic film layer. Further, in some embodiments, the siloxane monomer I has a structure represented by the following formula (3),
,R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17 And R 18 in the formula (3) are respectively and independently selected from hydrogen atoms or C 1-C4 hydrocarbon groups, at least one of R 10、R11 and R 12 is not hydrogen atoms, at least one of R 13、R14 and R 15 is not hydrogen atoms, at least one of R 16、R17 and R 18 is not hydrogen atoms, and p is an integer of 1-10. Further, in some embodiments, R 7、R8 and R 9 are each independently selected from a hydrogen atom or a methyl group, and R 10、R11、R12、R13、R14、R15、R16、R17 and R 18 are each independently selected from a methyl group or an ethyl group, further, in some embodiments, the siloxane monomer one is methacryloxypropyl tris (trimethylsiloxane) silane, further, in some embodiments, the siloxane monomer two has a structure represented by the following formula (2),
The R 5 is an olefinic group of C 1-C4 and the R 6 is an paraffinic group of C 1-C4, further, in some embodiments, the siloxane monomer two is 1,3,5, 7-tetravinyl-1, 3,5, 7-tetramethylcyclotetrasiloxane. In some embodiments of the present invention, the molar ratio of the first siloxane monomer to the second siloxane monomer is 1:10 to 10:1, and specifically, for example, 1:10, 2:10, 3:10, 4:10, 5:10, 6:10, 7:10, 8:10, 9:10, 10:10, 10:1, 10:2, 10:3, 10:4, 10:5, 10:6, 10:7, 10:8, 10:9, and the like may be used.
According to the preparation method of the organic silicon nanometer hydrophobic film layer, disclosed by the embodiment of the invention, the plasma is deposited on the surface of the substrate more uniformly by arranging the double electrodes suitable for discharging in the plasma reaction chamber and forming a more uniform electric field compared with a single electrode. The double electrode comprises a center electrode arranged at the center of the plasma reaction chamber and a cavity wall electrode arranged on the inner wall of the plasma reaction chamber, so that a uniform electric field is formed in the whole plasma reaction chamber during discharge.
In some embodiments, the method for preparing the organosilicon nano-hydrophobic film layer according to the embodiments of the invention prepares the film layer on the substrate by a film plating device shown in fig. 1. Referring to fig. 1, fig. 1 shows a schematic structure of a coating apparatus used in a preparation method according to an embodiment of the present invention. The coating apparatus comprises a plasma reaction chamber 1 adapted to receive a substrate 9. The plasma reaction chamber 1 comprises an inner wall 2. The plasma reaction chamber 1 comprises a double electrode adapted for discharge, said double electrode comprising a central electrode 3 and a cavity wall electrode 4, the central electrode 3 being arranged in the center of the plasma reaction chamber 1, the cavity wall electrode 4 being arranged in the inner wall 2 of the plasma reaction chamber 1.
In some embodiments, the central electrode 3 includes at least one cylindrical electrode, and the cavity wall electrode 4 includes at least one electrode plate.
In some embodiments, the central electrode 3 comprises two cylindrical electrodes (31, 32) sleeved together, one of the cylindrical electrodes is grounded, and the other cylindrical electrode is communicated with a power supply so as to form an electric field 33 between the two cylindrical electrodes (31, 32), and the gaseous siloxane monomer is activated into plasma in the electric field. The cavity wall electrode 4 comprises at least two electrode plates, wherein the electrode plates are communicated with one end of a power supply, the other end of the power supply is connected with a reaction cavity, and the reaction cavity is grounded.
In some embodiments, the central electrode 3 is a cylindrical electrode, the shape of the cavity wall electrode 4 corresponds to the shape of the plasma reaction chamber 1, for example, the plasma reaction chamber 1 is cylindrical, the corresponding cavity wall electrode 4 is cylindrical, and when the cavity wall electrode 4 comprises an electrode plate, the electrode plate is cylindrical; when the cavity wall electrode 4 includes at least two electrode plates, the at least two electrode plates are respectively arc-shaped plate-like and jointly form a cylinder shape.
In the preparation method of the organosilicon nano-hydrophobic membrane layer in the specific embodiments of the invention, in some specific embodiments, the cavity wall electrode 4 is provided with a plurality of pores so as to facilitate the gaseous siloxane monomer to pass through the pores and enter the plasma reaction chamber 1.
According to the preparation method of the organic silicon nanometer hydrophobic film layer in the specific embodiment of the invention, an air extracting device is arranged in the plasma reaction chamber 1 to adjust the pressure, in some specific embodiments, an air extracting column is arranged at the center of the plasma reaction chamber 1, a hole is arranged on the air extracting column and is communicated with a vacuum pump to extract the gas in the plasma reaction chamber 1, and the pressure of the plasma reaction chamber 1 is controlled. In some embodiments, the center electrode includes a first cylindrical electrode 31 and a second cylindrical electrode 32, and the second cylindrical electrode 32 is sleeved in the first cylindrical electrode 31. In some embodiments, the second cylindrical electrode 32 is provided with a plurality of holes, so as to serve as a pumping column and be grounded, the first cylindrical electrode 31 is sleeved on the outer side of the pumping column and is communicated with a power supply, and the first cylindrical electrode 31 is provided with a plurality of holes, so that gas can pass through the pumping column and be pumped out of the plasma reaction chamber 1.
In the preparation method of the organosilicon nano-hydrophobic membrane layer in the specific embodiments of the invention, in some specific embodiments, the first cylindrical electrode 31 is sleeved outside the second cylindrical electrode 32, and the first cylindrical electrode 31 and the cavity wall electrode 4 can be designed to be electrically connected with the same power supply or respectively electrically connected with two power supplies. In some embodiments, the first cylindrical electrode 31 and the cavity wall electrode 4 are electrically connected to the same power supply, so that when the power supply is turned on, the central electrode 3 and the cavity wall electrode 4 discharge simultaneously, which improves the discharge efficiency and the distribution uniformity of the formed electric field in the plasma reaction chamber 1, the electric field activated siloxane monomer is plasma, and the plasma performs chemical vapor deposition on the substrate surface 91 to form the organosilicon nano hydrophobic film layer.
With continued reference to fig. 1, a support 5 is disposed in the plasma reaction chamber 1 of the film plating apparatus, a support member 6 is disposed on the support 5, a support region 61 is disposed on the support member 6, and is suitable for supporting the substrate 9 disposed thereon, and in the process of preparing the organosilicon nano-film layer on the substrate surface 91, the support member 5 rotates around the central axis X of the support member 5 and the support member 6 rotates around the central axis Y of the support member 6, so as to drive the substrate 9 to rotate in the reaction chamber. In some embodiments, the central axis X of the support 5 is located in the center of the plasma reaction chamber 1.
In some embodiments, the support 6 is disposed around the support 5 by more than one layer, and more than 1 support 6 is disposed around the support 5, for example, 3 to 5 layers of the support 6 are disposed around the support 5, and 3 to 10 supports 6 are disposed on each layer, and the substrate 9 is disposed on the support 6, so as to further increase the space utilization efficiency of the plasma reaction chamber 1, so that the preparation of the silicone nano-hydrophobic film layer on the plurality of substrate surfaces 91 can be achieved simultaneously.
In some embodiments, the support 5 rotates around the central axis X of the support 5 to form a revolution, and the support 6 rotates around the central axis Y of the support 6 to form a rotation, so as to form a planetary rotation, that is, the substrate 9 placed on the support 6 rotates and revolves in the plasma reaction chamber 1, so as to provide coating conditions with higher consistency for all the substrates 9, thereby ensuring that all the substrates obtain a uniform film, so as to meet the requirement of industrialized mass production.
In some embodiments, the rotation speed of the support 5 is 1 to 10 rpm, specifically, for example, 1 rpm, 2 rpm, 3 rpm, 4 rpm, 6 rpm, 7 rpm, 9 rpm or 10 rpm, and the rotation speed of the support 6 is 1 to 10 rpm, specifically, for example, 1 rpm, 2 rpm, 3 rpm, 4 rpm, 6 rpm, 7 rpm, 9 rpm or 10 rpm, and the like.
With continued reference to fig. 1, a monomer release source 7 is provided on a sidewall of the plasma reaction chamber 1, which communicates with a monomer supply unit 8, the monomer release source 7 being provided with a monomer inlet 71 so that the monomer supply unit 8 provides siloxane-based monomers into the plasma reaction chamber 1 through the monomer inlet 71. During the coating process, the gaseous siloxane-based monomer 72 enters the plasma reaction chamber 1 through the monomer inlet 71. In some embodiments, the plurality of monomer inlets 71 are uniformly distributed on the sidewall of the plasma reaction chamber 1. The monomer inlet 71 may be provided on the sidewall adjacent to the support 6 to reduce the distance of the gaseous siloxane-based monomer 72 from the substrate 9 and reduce the time for chemical vapor deposition of the siloxane-based monomer on the substrate surface 91, thereby increasing the coating speed.
It should be noted that the film plating apparatus shown in fig. 1 is merely an example of an apparatus used in the preparation method of the silicone nano-hydrophobic film layer according to the embodiment of the present invention, and is not a limitation of the film plating apparatus used in the preparation method of the embodiment of the present invention. Based on the preparation method of the specific embodiment of the invention, other coating equipment can be selected for coating.
According to the preparation method of the organic silicon nanometer hydrophobic film layer, in some specific embodiments, a gauze is arranged between a monomer air inlet and a substrate, and due to the flow guiding effect of the gauze, the air flow distribution of the gaseous siloxane monomer entering the gauze is more uniform, so that the surface of the substrate is in contact with the uniform gaseous siloxane monomer serving as a coating material, and in some specific embodiments, the gauze is arranged in a manner of directly wrapping the gauze on a substrate support. In some embodiments, the mesh size of the gauze is 10-100 mesh, specifically 10 mesh, 20 mesh, 30 mesh, 50 mesh, 60 mesh, 70 mesh, 80 mesh, 90 mesh, 100 mesh, etc., and the mesh size may be adjusted according to the specific siloxane monomer type.
In the preparation method of the organic silicon nanometer hydrophobic film layer in the embodiment of the invention, in some embodiments, the water contact angle of the organic silicon nanometer hydrophobic film layer is not less than 105 degrees, and can be 105°、106°、107°、108°、109°、110°、111°、112°、113°、114°、115°、116°、117°、118°、119°、120°、125°、130°、135°、140°、145° degrees, 150 degrees or the like specifically.
In some embodiments, the thickness of the organic silicon nano hydrophobic film layer is 10-100 nm, and may be, for example, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, etc.
In the preparation method of the organic silicon nanometer hydrophobic film layer in the specific embodiments of the invention, in some specific embodiments, the flow rate of the siloxane monomer is 10-2000 mu L/min, and can be 50μL/min、100μL/min、150μL/min、160μL/min、200μL/min、300μL/min、400μL/min、500μL/min、1000μL/min、1500μL/min or 2000 mu L/min, for example; the temperature of the plasma reaction chamber is controlled to be 30-60 ℃, specifically, for example, 30 ℃, 40 ℃, 45 ℃,50 ℃, 55 ℃ or 60 ℃ and the like; the monomer gasification temperature is 50 to 180℃and specifically, for example, 50℃60℃70℃75℃80℃85℃90℃95℃100℃110℃120℃130℃140℃150℃160℃170℃180℃180℃and the like, and gasification is carried out under vacuum.
In some embodiments, to further improve the bonding force of the organosilicon nano-hydrophobic film layer, in some embodiments, the substrate is pretreated by adopting continuous plasma before coating, for example, a specific pretreatment mode is to vacuumize to 10-200 millitorr, and one or more mixed gases of gases He, ar and O 2 are introduced, and plasma discharge is started to pretreat the substrate, or modes of heat, oxygen or high-energy radiation and the like are adopted.
In the preparation method of the organic silicon nanometer hydrophobic film layer in the specific embodiments, in some specific embodiments, continuous discharge or pulse discharge is adopted in the pretreatment stage and the film coating stage.
In some embodiments, the central electrode and the cavity wall electrode are electrically connected with the same power supply, and in the pretreatment stage, when continuous discharge is used, the discharge power is 50-600W, specifically, for example, 50W, 100W, 120W, 140W, 160W, 180W, 190W, 200W, 210W, 220W, 230W, 240W, 250W, 260W, 270W, 280W, 290W, 300W, 400W, 500W or 600W, etc.; the discharge time is 30 to 2400s, and specifically, for example, 30s, 60s, 100s, 200s, 300s, 400s, 500s, 600s, 1000s, 1200s, 1500s, 1800s, 2400s, or the like can be used. When pulse discharge is used, the pulse duty ratio may be, for example, 0.1% to 80%, specifically 0.1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% or 80%, or the like; the pulse frequency is 10 to 500Hz, and specifically, for example, 10Hz, 20Hz, 25Hz, 30Hz, 35Hz, 40Hz, 45Hz, 50Hz, 55Hz, 60Hz, 70Hz, 80Hz, 90Hz, 100Hz, 200Hz, 300Hz, 400Hz, 500Hz, or the like; the discharge power is 10 to 500W, and may be 10W、20W、30W、40W、50W、60W、70W、80W、90W、100W、120W、140W、160W、180W、190W、200W、210W、220W、230W、240W、250W、260W、270W、280W、290W、300W、400W、500W or the like, for example; the discharge time is 30 to 2400s, and specifically, for example, 30s, 60s, 100s, 200s, 300s, 400s, 500s, 600s, 1000s, 1200s, 1500s, 1800s, 2400s, or the like can be used.
In some embodiments, the central electrode and the cavity wall electrode are electrically connected with the same power supply, and in the film plating stage, when continuous discharge is used, the discharge power is 10-300W, specifically, for example, 10W、20W、30W、40W、50W、60W、70W、80W、90W、100W、120W、140W、160W、180W、190W、200W、210W、220W、230W、240W、250W、260W、270W、280W、290W or 300W and the like; the discharge time is 60 to 36000s, specifically, 60s, 100s, 200s, 300s, 400s, 500s, 600s, 1000s, 2000s, 3000s, 5000s, 10000s, 15000s, 20000s, 25000s, 30000s, 36000s, or the like, for example. When pulse discharge is used, the pulse duty ratio may be 0.1 to 80%, specifically, for example, 0.1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% or 80%, or the like; the pulse frequency is 10 to 500Hz, and specifically, for example, 10Hz, 20Hz, 25Hz, 30Hz, 35Hz, 40Hz, 45Hz, 50Hz, 55Hz, 60Hz, 70Hz, 80Hz, 90Hz, 100Hz, 200Hz, 250Hz, 300Hz, 400Hz, 500Hz, or the like; the discharge power is 10 to 400W, and may be 10W、20W、30W、40w、50w、60w、70w、80w、90w、100w、120W、140W、160W、180W、190W、200W、210W、220W、230W、240W、250W、260W、270W、280W、290W、300W or 400W, for example; the discharge time is 200 to 36000s, specifically, for example, 200s, 500s, 1000s, 2000s, 3000s, 3600s, 4000s, 5000s, 6000s, 7000s, 7200s, 10000s, 15000s, 20000s, 25000s, 30000s, 36000s, or the like.
In some embodiments, the plasma discharge mode may be any of various existing discharge modes, for example, electrodeless discharge (such as rf inductively coupled discharge, microwave discharge), single electrode discharge (such as corona discharge, plasma jet formed by unipolar discharge), double electrode discharge (such as dielectric barrier discharge, bare electrode rf glow discharge), and multi-electrode discharge (such as discharge using a floating electrode as a third electrode).
In some embodiments, the substrate is various plastics, fabrics, glass, electrical components, optical instruments, or the like. In particular, the electrical component may be a Printed Circuit Board (PCB), an electronic product, or an electronic assembly semi-finished product, etc. In some embodiments, the substrate is an electronic or electrical component, and when the substrate is an electronic product, for example, the substrate may be a mobile phone, a tablet computer, a keyboard, an electronic reader, a wearable device, a display, an earphone, a USB data line, a USB interface, a sound-transmitting network, an ear muff, a headband, or the like, as a specific non-limiting example. The substrate may also be any suitable electrical component of an electrical assembly, in particular the electrical component may be a resistor, a capacitor, a transistor, a diode, an amplifier, a relay, a transformer, a battery, a fuse, an integrated circuit, a switch, an LED display, a piezoelectric element, an optoelectronic component or an antenna or an oscillator, etc.
Embodiments of the present invention also provide an organosilicon nano-hydrophobic film layer, which in some embodiments is prepared by the preparation method of the organosilicon nano-hydrophobic film layer described above.
Embodiments of the present invention also provide a device having at least a portion of its surface with a silicone nano-hydrophobic film layer as described above, and in some embodiments, only a portion or all of its surface is coated with a protective coating as described above. In some embodiments, the device is an electrical component, an optical instrument, an electronic or electrical component, or the like, as previously described.
The invention is further illustrated by the following examples.
Examples
Description of the test methods
Coating water antenna: the test was performed according to the GB/T3047-2013 standard.
Film thickness test: detection was performed using a U.S. FILMETRICS F-UV-film thickness gauge.
Film forming speed test: and calculating the thickness of the film formed in unit time according to the thickness of the film formed in a certain time.
Abrasion resistance test: the abrasion resistance test was carried out on an abrasion tester, the friction material was a dust-free cloth, and the water contact angles before and after the abrasion were measured 1000 times under a pressure of 1N and a condition of 50 cycles/min.
Example 1
Placing a Si sheet and a glass substrate in a plasma reaction chamber, placing the substrate on a support piece of a bracket, and wrapping the support piece by using a 20-mesh gauze; the plasma reaction chamber is internally provided with a double electrode, wherein the double electrode is a central electrode and a chamber wall electrode which are electrically connected with the same power supply and used for discharging into the chamber;
Vacuumizing the chamber to 20 millitorr, and introducing helium with the flow of 80sccm and the chamber temperature of 45 ℃;
Maintaining the air pressure of the chamber at 20 millitorr, maintaining the helium flow at 80sccm, starting the support and the support to rotate, performing planetary motion on the substrate, enabling the support to rotate at 2 rpm, enabling the support to rotate at 3 rpm, starting the double-electrode plasma to continuously discharge, enabling the discharge power to be 100W, and continuously discharging for 600s, so as to pretreat the substrate;
then, monomer decamethyl tetrasiloxane is gasified at the temperature of 85 ℃ and then is led into a plasma chamber, the pressure of the chamber is kept to be 20 millitorr, the flow rate of helium is kept to be 80sccm, a bracket and a supporting piece are kept to rotate, a double-electrode radio-frequency plasma discharge is started, the energy output mode of radio frequency is pulse, plasma chemical vapor deposition is carried out on the surface of a substrate, wherein the pulse duty ratio is 25%, the pulse frequency is 200Hz, the pulse discharge power is 120W, the flow rate of the monomer is 160 mu L/min, and the reaction time is 3600s;
after the coating was completed, the chamber was returned to normal pressure by charging compressed air, the coated substrate Si sheet and glass were taken out, the film thickness of the Si sheet was measured as shown in Table 1 below, and the abrasion resistance of the glass was measured as shown in Table 2 below.
Comparative example 1
Placing a Si sheet and a glass substrate in a plasma reaction chamber, placing the substrate on a support piece of a bracket, and wrapping the support piece by using a 20-mesh gauze; a central electrode electrically connected with a power supply is arranged in the plasma reaction chamber and used for discharging into the chamber;
Vacuumizing the chamber to 20 millitorr, and introducing helium with the flow of 80sccm and the chamber temperature of 45 ℃;
Maintaining the air pressure of the chamber at 20 millitorr, maintaining the helium flow at 80sccm, starting the support and the support to rotate, performing planetary motion on the substrate, enabling the support to rotate at 2 rpm, enabling the support to rotate at 3 rpm, starting the central electrode to continuously discharge plasma, enabling the discharge power to be 100W, and continuously discharging for 600s, so as to pretreat the substrate;
then, monomer decamethyl tetrasiloxane is gasified at the temperature of 85 ℃ and then is led into a plasma chamber, the pressure of the chamber is kept to be 20 millitorr, the flow rate of helium is kept to be 80sccm, a bracket and a supporting piece are kept to rotate, a central electrode radio frequency plasma discharge is started, the energy output mode of radio frequency is pulse, plasma chemical vapor deposition is carried out on the surface of a substrate, wherein the pulse duty ratio is 25%, the pulse frequency is 200Hz, the pulse discharge power is 120W, the flow rate of the monomer is 160 mu L/min, and the reaction time is 3600s;
after the coating was completed, the chamber was returned to normal pressure by charging compressed air, the coated substrate Si sheet and glass were taken out, the film thickness of the Si sheet was measured as shown in Table 1 below, and the abrasion resistance of the glass was measured as shown in Table 2 below.
Example 2
Placing a Si sheet and a glass substrate in a plasma chamber, placing the substrate on a support piece of a bracket, and wrapping the support piece by using a 30-mesh gauze; the plasma reaction chamber is internally provided with a double electrode, wherein the double electrode is a central electrode and a chamber wall electrode which are electrically connected with the same power supply and used for discharging into the chamber;
Vacuumizing the chamber to 50 millitorr, and introducing helium gas with the flow of 70sccm and the chamber temperature of 50 ℃;
Maintaining the air pressure of the chamber at 50 millitorr, maintaining the helium flow at 70sccm, starting the rotation of the support and the supporting piece, performing planetary motion on the substrate, wherein the rotation speed of the support is 1 revolution/min, the rotation speed of the supporting piece is 1.5 revolution/min, starting the continuous discharge of the double-electrode plasma, the discharge power is 300W, and continuously discharging for 300s, so as to pretreat the substrate;
Then, monomer octamethyltrisiloxane is gasified at the temperature of 75 ℃ and then is led into a plasma chamber, the pressure of the chamber is kept at 50 millitorr, the flow rate of helium is kept at 70sccm, a bracket and a supporting piece are kept to rotate, a double-electrode radio-frequency plasma discharge is started, the energy output mode of radio frequency is pulse, plasma chemical vapor deposition is carried out on the surface of a substrate, wherein the pulse duty ratio is 50%, the pulse frequency is 100Hz, the pulse discharge power is 180W, the flow rate of the monomer is 150 mu L/min, and the reaction time is 3600s;
after the coating was completed, the chamber was returned to normal pressure by charging compressed air, the coated substrate Si sheet and glass were taken out, the film thickness of the Si sheet was measured as shown in Table 1 below, and the abrasion resistance of the glass was measured as shown in Table 2 below.
Comparative example 2
Placing a Si sheet and a glass substrate in a plasma chamber, placing the substrate on a support piece of a bracket, and wrapping the support piece by using a 30-mesh gauze; a central electrode electrically connected with a power supply is arranged in the plasma reaction chamber and used for discharging into the chamber;
Vacuumizing the chamber to 50 millitorr, and introducing helium gas with the flow of 70sccm and the chamber temperature of 50 ℃;
Maintaining the air pressure of the chamber at 50 millitorr, maintaining the helium flow at 70sccm, starting the rotation of the support and the supporting piece, performing planetary motion on the substrate, wherein the rotation speed of the support is 1 revolution/min, the rotation speed of the supporting piece is 1.5 revolution/min, starting the continuous discharge of the central electrode plasma, the discharge power is 300W, and continuously discharging for 300s, so as to pretreat the substrate;
Then, monomer octamethyltrisiloxane is gasified at the temperature of 75 ℃ and then is led into a plasma chamber, the pressure of the chamber is kept at 50 millitorr, the flow rate of helium is kept at 70sccm, a bracket and a supporting piece are kept to rotate, a central electrode radio frequency plasma discharge is started, the energy output mode of radio frequency is pulse, plasma chemical vapor deposition is carried out on the surface of a substrate, wherein the pulse duty ratio is 50%, the pulse frequency is 100Hz, the pulse discharge power is 180W, the flow rate of the monomer is 150 mu L/min, and the reaction time is 3600s;
after the coating was completed, the chamber was returned to normal pressure by charging compressed air, the coated substrate Si sheet and glass were taken out, the film thickness of the Si sheet was measured as shown in Table 1 below, and the abrasion resistance of the glass was measured as shown in Table 2 below.
Example 3
Placing a Si sheet and a glass substrate in a plasma chamber, placing the substrate on a support piece of a bracket, and wrapping the support piece by using a 50-mesh gauze; the plasma reaction chamber is internally provided with a double electrode, wherein the double electrode is a central electrode and a chamber wall electrode which are electrically connected with the same power supply and used for discharging into the chamber;
Vacuumizing the chamber to 100 millitorr, and introducing helium gas with the flow of 50sccm and the chamber temperature of 55 ℃;
Maintaining the air pressure of the chamber at 100 millitorr, maintaining the helium flow at 50sccm, starting the rotation of the support and the supporting piece, performing planetary motion on the substrate, wherein the rotation speed of the support is 2 revolutions per minute, the rotation speed of the supporting piece is 2.5 revolutions per minute, starting the pulse discharge of the double-electrode plasma, the pulse duty ratio is 60%, the pulse frequency is 300Hz, the discharge power is 300W, and continuously discharging for 300s, so as to pretreat the substrate;
Then, monomer tetra (trimethylsiloxy) silane is gasified at the gasification temperature of 95 ℃ and then is introduced into a plasma chamber, the pressure of the chamber is kept at 100 millitorr, the flow of helium is kept at 50sccm, a support and a support piece are kept to rotate, a double-electrode radio-frequency plasma discharge is started, the energy output mode of radio frequency is pulse, plasma chemical vapor deposition is carried out on the surface of a substrate, wherein the pulse duty ratio is 35%, the pulse frequency is 250Hz, the pulse discharge power is 200W, the flow of the monomer is 200 mu L/min, and the reaction time is 3600s;
after the coating was completed, the chamber was returned to normal pressure by charging compressed air, the coated substrate Si sheet and glass were taken out, the film thickness of the Si sheet was measured as shown in Table 1 below, and the abrasion resistance of the glass was measured as shown in Table 2 below.
Comparative example 3
Placing a Si sheet and a glass substrate in a plasma chamber, placing the substrate on a support piece of a bracket, and wrapping the support piece by using a 50-mesh gauze; a central electrode electrically connected with a power supply is arranged in the plasma reaction chamber and used for discharging into the chamber;
Vacuumizing the chamber to 100 millitorr, and introducing helium gas with the flow of 50sccm and the chamber temperature of 55 ℃;
Maintaining the air pressure of the chamber at 100 millitorr, maintaining the helium flow at 50sccm, starting the rotation of the support and the supporting piece, performing planetary motion on the substrate, wherein the rotation speed of the support is 2 revolutions per minute, the rotation speed of the supporting piece is 2.5 revolutions per minute, starting the plasma pulse discharge of the central electrode, the pulse duty ratio is 60%, the pulse frequency is 300Hz, the discharge power is 300W, and continuously discharging for 300s, so as to pretreat the substrate;
Then, monomer tetra (trimethylsiloxy) silane is gasified at the gasification temperature of 95 ℃ and then is introduced into a plasma chamber, the pressure of the chamber is kept at 100 millitorr, the flow of helium is kept at 50sccm, a bracket and a support piece are kept to rotate, a central electrode radio frequency plasma discharge is started, the energy output mode of radio frequency is pulse, plasma chemical vapor deposition is carried out on the surface of a substrate, wherein the pulse duty ratio is 35%, the pulse frequency is 250Hz, the pulse discharge power is 200W, the flow of the monomer is 200 mu L/min, and the reaction time is 3600s;
after the coating was completed, the chamber was returned to normal pressure by charging compressed air, the coated substrate Si sheet and glass were taken out, the film thickness of the Si sheet was measured as shown in Table 1 below, and the abrasion resistance of the glass was measured as shown in Table 2 below.
TABLE 1 film thickness test results
A, B, C in table 1 represents the positions of the Si sheet substrate farthest to nearest the rotation axis of the support, respectively.
From the film thickness test results of examples 1 to 3 shown above, it is understood that in examples 1 to 3, the substrate was rotated by the rotation of the center electrode and the cavity wall electrode, while in comparative examples 1 to 3, the discharge was performed only by the center electrode, the coating thicknesses at different positions on the substrate surface of examples 1 to 3 were smaller than those in comparative examples 1 to 3, the film thickness distribution was more uniform, and the uniformity and consistency of the film layers were significantly improved.
Meanwhile, according to the average film forming speed of the film thickness calculation A, B, C, as shown in table 1, the film forming speed in the embodiment 1-3 is improved by 1.5-2 times compared with that in the comparative embodiment 1-3, the center electrode and the cavity wall electrode are used for discharging simultaneously in the embodiment 1-3, the plasma forming speed is faster, the chemical vapor deposition of the monomer on the surface of the substrate is facilitated, and therefore the substrate film coating can be completed more quickly, and the film coating efficiency is improved.
TABLE 2 results of abrasion resistance test
Water contact angle/° before rubbing Water contact angle/° after rubbing
Example 1 108 91
Comparative example 1 110 83
Example 2 108 88
Comparative example 2 109 78
Example 3 107 89
Comparative example 3 106 75
From the results of table 2 above, it can be seen that the water contact angle of the coating film layer in examples 1-3 after rubbing was substantially uniform compared to comparative examples 1-3 by discharging the central electrode and the cavity wall electrode and simultaneously rotating the stent and the support to rotate the substrate, and that the water contact angle of the coating film layer in examples 1-3 after rubbing was significantly higher than that in comparative examples 1-3, indicating that the coating film layer in examples 1-3 had more excellent abrasion resistance.
Although the present invention is disclosed above, the present invention is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention, and the scope of the invention should be assessed accordingly to that of the appended claims.

Claims (20)

1. The preparation method of the organic silicon nanometer hydrophobic film layer is characterized by comprising the following steps of:
Placing a substrate in a plasma reaction chamber, wherein a double electrode suitable for discharging is arranged in the plasma reaction chamber, and the double electrode comprises: a center electrode arranged at the center of the plasma reaction chamber and a cavity wall electrode arranged on the inner wall of the plasma reaction chamber;
Introducing gaseous siloxane monomers into the plasma reaction chamber through the monomer air inlet, starting the double electrodes to discharge plasma in the plasma reaction chamber, and forming the organosilicon nano hydrophobic film layer on the surface of the substrate through plasma chemical vapor deposition of the siloxane monomers;
the siloxane monomer comprises at least one structure shown in the following formula (1) or (2),
In the formula (1) or (2), R 1、R2、R3、R5 and R 6 are respectively and independently selected from a hydrogen atom, halogen, substituted or unsubstituted alkyl of C 1-C12, substituted or unsubstituted alkoxy of C 1-C12 and substituted or unsubstituted alkyl siloxy of C 1-C12, at least one of R 1、R2 and R 3 is not a hydrogen atom, at least one of R 5 or R 6 is not a hydrogen atom, R 4 is substituted or unsubstituted alkyl of C 1-C12 or substituted or unsubstituted alkyl silicon of C 1-C12, n is an integer of 1-100, and m is an integer of 3-10.
2. The method of claim 1, wherein the center electrode comprises at least one cylindrical electrode and the chamber wall electrode comprises at least one electrode plate.
3. The method of claim 2, wherein the central electrode and the cavity wall electrode are electrically connected to the same power source.
4. The method for preparing the organosilicon nano-hydrophobic membrane layer according to claim 1, wherein the plasma discharge is pulse discharge, the pulse duty ratio is 0.1-80%, the pulse frequency is 10-500 Hz, the discharge power is 10-400W, and the discharge time is 200-36000 s.
5. The method for preparing the organic silicon nanometer hydrophobic film layer according to claim 1, further comprising:
and a gauze is arranged between the monomer air inlet and the substrate, and the gaseous siloxane monomer passes through the gauze and then is subjected to plasma chemical vapor deposition on the surface of the substrate to form the organosilicon nano hydrophobic film layer.
6. The method for preparing a nano hydrophobic membrane layer of organic silicon according to claim 5, wherein the mesh size of the gauze is 10-100 mesh.
7. The method for preparing a nano hydrophobic membrane layer of organic silicon according to claim 1, wherein the flow rate of the siloxane monomer is 10-2000 μl/min.
8. The method for preparing a nano hydrophobic membrane layer of organic silicon according to claim 1, wherein a support is arranged in the plasma reaction chamber, a supporting piece is arranged on the support, the substrate is arranged on the supporting piece, and the substrate is driven to rotate in the plasma reaction chamber by rotating the support around a central axis of the support and rotating the supporting piece around the central axis of the supporting piece.
9. The method for preparing a nano hydrophobic membrane layer of organic silicon according to claim 8, wherein the rotation speed of the support is 1-10 rpm, and the rotation speed of the support is 1-10 rpm.
10. The method for producing a silicone nano-hydrophobic film layer according to claim 1, wherein the water contact angle of the silicone nano-hydrophobic film layer is not less than 105 °.
11. The method for preparing the organic silicon nanometer hydrophobic film layer according to claim 1, further comprising: before the chemical vapor deposition, vacuumizing to 10-200 millitorr, introducing one or more mixed gases of He, ar and O 2, and starting plasma discharge to pretreat the substrate.
12. The method for preparing an organosilicon nano-hydrophobic membrane layer according to claim 1, wherein R 1、R2、R3、R5 and R 6 are each independently selected from methyl or ethyl, R 4 is methyl, ethyl or trimethylsilyl, and n is an integer of 2 to 10.
13. The method of claim 1, wherein the siloxane-based monomer comprises a first siloxane monomer and a second siloxane monomer, wherein the first siloxane monomer has one unsaturated double bond, and the second siloxane monomer has at least two unsaturated double bonds.
14. The method for preparing a nano hydrophobic membrane layer of organic silicon according to claim 13, wherein the siloxane monomer one has a structure shown in the following formula (3),
,R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17 And R 18 in the formula (3) are respectively and independently selected from hydrogen atoms or C 1-C4 hydrocarbon groups, at least one of R 10、R11 and R 12 is not hydrogen atoms, at least one of R 13、R14 and R 15 is not hydrogen atoms, at least one of R 16、R17 and R 18 is not hydrogen atoms, and p is an integer of 1-10.
15. The method for preparing a nano hydrophobic membrane layer according to claim 14, wherein R 7、R8 and R 9 are independently selected from hydrogen atom or methyl group, and R 10、R11、R12、R13、R14、R15、R16、R17 and R 18 are independently selected from methyl group or ethyl group.
16. The method of claim 15, wherein the siloxane monomer one is methacryloxypropyl tris (trimethylsiloxy) silane.
17. The method for preparing a nano hydrophobic membrane layer of organic silicon according to claim 13, wherein the second siloxane monomer has a structure shown in formula (2), R 5 is an olefine group of C 1-C4, and R 6 is an alkane group of C 1-C4.
18. The method for preparing a nano hydrophobic membrane layer of organic silicon according to claim 17, wherein the second siloxane monomer is 1,3,5, 7-tetravinyl-1, 3,5, 7-tetramethyl cyclotetrasiloxane.
19. An organosilicon nano-hydrophobic membrane layer, characterized in that the organosilicon nano-hydrophobic membrane layer is prepared by the preparation method of the organosilicon nano-hydrophobic membrane layer according to any one of claims 1-18.
20. A device characterized in that at least part of the surface of the device has the silicone nano-hydrophobic film layer of claim 19.
CN202211246102.2A 2022-10-12 2022-10-12 Organosilicon nano hydrophobic film layer and preparation method thereof Pending CN117904607A (en)

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JPS61110768A (en) * 1984-11-05 1986-05-29 Sharp Corp Device for manufacturing amorphous silicon photosensitive body
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