CN117427856A - Siloxane hydrophobic film and preparation method thereof - Google Patents

Abstract

A specific embodiment of the present invention provides a silicone hydrophobic film layer and a preparation method thereof. The silicone hydrophobic film layer is formed by plasma polymerization and deposition of silicone monomers. During the preparation process, A gauze is set between the body vapor inlet and the substrate, and at the same time, the substrate rotates in the reaction chamber, effectively overcoming the direct entry of siloxane monomer vapor into the plasma chamber for deposition at different locations on the substrate surface. The problem of large differences in coating thickness.

Description

Silicone hydrophobic film layer and preparation method thereof

Technical field

The invention belongs to the field of chemical protective coatings, and specifically relates to a silicone hydrophobic film layer and a preparation method thereof.

Background technique

Hydrophobicity generally requires the water contact angle on the surface of the material to be greater than 90°. Currently, widely used hydrophobic materials are divided into two types: silicone and fluorine-containing materials. Among them, fluorine-containing materials have been widely used because of their excellent hydrophobic and oleophobic properties. application. On a smooth surface, fluorine-containing materials can prepare a hydrophobic film layer with a maximum water contact angle of about 120°. However, fluorine-containing materials have poor friction resistance, are expensive, resistant to high temperatures and not easy to degrade, and are carcinogenic, reproductively toxic, and developmental. Due to various toxicological disadvantages such as toxicity and neurotoxicity, its application has been limited. The EU POPs regulations require the ban on the use of perfluorooctanoic acid (PFOA), perfluorooctane sulfonate (PFOS) and their derivatives, and the US Packaging Act TPCH requires that perfluoroalkyl and polyfluoroalkyl substances (PFAS) must not be detected. Therefore, siloxane materials are the first choice to replace fluorine-containing materials, and people are paying more and more attention to the research of silane hydrophobic materials.

Plasma activation reaction organic monomer gas is used to deposit on the surface of the substrate. This method is suitable for various substrates, and the deposited polymer protective coating is uniform, the coating preparation temperature is low, the coating thickness is thin, and the stress is small. There is almost no damage to the surface of the substrate and almost no impact on the performance of the substrate. There have been relevant studies that used plasma deposition of siloxane monomer gas to form a hydrophobic protective film layer on the substrate. However, the existing commonly used plasma During the coating process, when the coating is deposited with silicone monomer gas, the thickness of the coating at different locations on the surface of the substrate is likely to vary greatly, which will affect the overall protective performance of the coating.

Contents of the invention

The specific embodiment of the present invention provides a silicone hydrophobic film layer and a preparation method thereof. The specific scheme is as follows:

A method for preparing a silicone hydrophobic film layer, including the following steps:

Place the substrate in the plasma reaction chamber;

A gauze is provided between the monomer steam inlet and the substrate. The silicone monomer steam is introduced into the plasma reaction chamber through the steam inlet, and the plasma discharge is started. The substrate is reacting Rotating motion in the chamber, the monomer vapor passes through the gauze and is deposited by plasma chemical vapor deposition on the surface of the substrate to form the silicone hydrophobic film layer.

Optionally, the silicone monomer includes at least one structure represented by the following formula (1) or (2),

In formula (1) or (2), R ₁ , R ₂ , R ₃ , R ₅ and R ₆ are independently selected from hydrogen atoms, C ₁ -C ₁₂ substituted or unsubstituted hydrocarbon groups, C ₁ -C ₁₂ A substituted or unsubstituted hydrocarbyloxy group, or a C ₁ -C ₁₂ substituted or unsubstituted hydrocarbyl siloxy group, at least one of R ₁ , R ₂ and R ₃ is not a hydrogen atom, and the R ₅ or R ₆ At least one of them is not a hydrogen atom, R ₄ is a C ₁ -C ₁₂ substituted or unsubstituted hydrocarbon group, or a C ₁ -C ₁₂ substituted or unsubstituted hydrocarbon group silyl group, n is an integer from 1 to 100, m is 3- An integer of 10.

Optionally, the R ₁ , R ₂ , R ₃ , R ₅ and R ₆ are independently selected from methyl or ethyl, R ₄ is methyl, ethyl or trimethylsilyl, and the n is an integer from 2 to 10.

Optionally, the siloxane monomer includes siloxane monomer one and siloxane monomer two, wherein the siloxane monomer one has an unsaturated double bond, and the siloxane monomer two has At least two unsaturated double bonds.

Optionally, the siloxane monomer has a structure shown in the following formula (3),

In formula (3), R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are independently selected from hydrogen atoms or C ₁ -C ₄ hydrocarbon group, at least one of R ₁₀ , R ₁₁ and R ₁₂ is not a hydrogen atom, at least one of R ₁₃ , R ₁₄ and R ₁₅ is not a hydrogen atom, at least one of R ₁₆ , R ₁₇ and R ₁₈ is not a hydrogen atom. One is not a hydrogen atom, and p is an integer from 1 to 10.

Optionally, the R ₇ , R ₈ and R ₉ are each independently selected from a hydrogen atom or a methyl group, and the R ₁₀ , R ₁₁ , R 12 , R ₁₃ , R ₁₄ , _{R 15 ,} R ₁₆ , R ₁₇ and R ₁₈ are each independently selected from methyl or ethyl.

Optionally, the siloxane monomer is methacryloyloxypropyltris(trimethylsiloxanyl)silane.

Optionally, the siloxane monomer two has the structure shown in formula (2), the R ₅ is a C ₁ -C ₄ alkenyl group, and the R ₆ is a C ₁ -C ₄ alkane group.

Optionally, the second siloxane monomer is 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane.

Optionally, the flow rate of the silicone monomer vapor is 10-2000ul/min.

Optionally, the mesh size of the gauze is 10-500 mesh.

Optionally, a support is provided in the reaction chamber, a support is provided on the support, the substrate is placed on the support, and the support is rotated around the central axis of the support and the support is rotated around the central axis of the support. The rotation of the central axis of the support member drives the substrate to rotate in the reaction chamber.

Optionally, the rotation speed of the bracket is 1-10 rpm, and the rotation speed of the support member is 1-10 rpm.

Optionally, the water contact angle of the silicone hydrophobic film layer is greater than 100°.

Optionally, before the chemical vapor deposition, the vacuum is evacuated to 10-200 mTorr, and one or more mixed gases of He, Ar, and _O2 are introduced, and plasma discharge is started to ignite the substrate. Materials are pre-treated.

A silicone hydrophobic film layer, the silicone hydrophobic film layer is prepared by the above-mentioned preparation method of the silicone hydrophobic film layer.

A device, at least part of the surface of the device is provided with the above-mentioned silicone hydrophobic film layer.

A siloxane hydrophobic film layer, the siloxane hydrophobic film layer is a plasma formed by contacting a substrate with a plasma of a siloxane monomer including siloxane monomer one and siloxane monomer two. A body polymerization coating is provided, wherein the siloxane monomer one has one unsaturated double bond, and the siloxane monomer two has at least two unsaturated double bonds.

Optionally, the siloxane monomer has a structure shown in the following formula (3),

In formula (3), R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are independently selected from hydrogen atoms or C ₁ -C ₄ hydrocarbon group, at least one of R ₁₀ , R ₁₁ and R ₁₂ is not a hydrogen atom, at least one of R ₁₃ , R ₁₄ and R ₁₅ is not a hydrogen atom, at least one of R ₁₆ , R ₁₇ and R ₁₈ is not a hydrogen atom. One is not a hydrogen atom, and p is an integer from 1 to 10.

Optionally, the R ₇ , R ₈ and R ₉ are each independently selected from a hydrogen atom or a methyl group, and the R ₁₀ , R ₁₁ , R 12 , R ₁₃ , R ₁₄ , _{R 15 ,} R ₁₆ , R ₁₇ and R ₁₈ are each independently selected from methyl or ethyl.

Optionally, the siloxane monomer is methacryloyloxypropyltris(trimethylsiloxanyl)silane.

Optionally, the siloxane monomer two has the structure shown in the following formula (2),

The R ₅ is a C ₁ -C ₄ alkenyl group, and the R ₆ is a C ₁ -C ₄ alkane group.

Optionally, the second siloxane monomer is 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane.

A device, at least part of the surface of the device has the above-mentioned silicone hydrophobic film layer.

Specific embodiments of the present invention provide a siloxane hydrophobic film layer and a preparation method thereof. The siloxane hydrophobic film layer is formed by plasma polymerization and deposition of siloxane monomers. During the preparation process, the monomer vapor is added to the A gauze is arranged between the air port and the substrate, and at the same time, the substrate rotates in the reaction chamber, so that the siloxane monomer vapor can be uniformly deposited on the surface of the substrate, effectively overcoming the siloxane monomer The direct entry of steam into the plasma chamber for deposition causes large differences in coating thickness at different locations on the substrate surface.

Detailed ways

The inventor of the present invention discovered during research that, probably due to the slow diffusion of siloxane monomer gas, when the siloxane monomer vapor directly enters the plasma chamber and is excited by the plasma to polymerize and deposit on the substrate to form a film layer, There are many differences in coating thickness at different locations on the surface of the substrate. By setting a gauze between the monomer vapor inlet and the substrate, and allowing the substrate to rotate in the reaction chamber, the silicone monomer can be The body is evenly distributed at different positions on the surface of the substrate, thereby effectively reducing the thickness difference of the coating. Therefore, a specific embodiment of the present invention provides a method for preparing the following silicone hydrophobic film layer, which includes the following steps:

Place the substrate in the plasma reaction chamber;

A gauze is provided between the monomer steam inlet and the substrate. The silicone monomer steam is introduced into the plasma reaction chamber through the steam inlet, and the plasma discharge is started. The substrate is reacting Rotating motion in the chamber, the monomer vapor passes through the gauze and is deposited by plasma chemical vapor deposition on the surface of the substrate to form the silicone hydrophobic film layer.

The preparation method of the silicone hydrophobic film layer according to the specific embodiment of the present invention. In some specific embodiments, the silicone monomer includes at least one structure represented by the following formula (1) or (2),

In formula (1) or (2), R ₁ , R ₂ , R ₃ , R ₅ and R ₆ are independently selected from hydrogen atoms, C ₁ -C ₁₂ substituted or unsubstituted hydrocarbon groups, C ₁ -C ₁₂ A substituted or unsubstituted hydrocarbyloxy group, or a C ₁ -C ₁₂ substituted or unsubstituted hydrocarbyl siloxy group, at least one of R ₁ , R ₂ and R ₃ is not a hydrogen atom, and the R ₅ or R ₆ At least one of them is not a hydrogen atom, R ₄ is a C ₁ -C ₁₂ substituted or unsubstituted hydrocarbon group, or a C ₁ -C ₁₂ substituted or unsubstituted hydrocarbon group silyl group, n is an integer from 1 to 100, m is 3- An integer of 10. In specific embodiments of the present invention, the hydrocarbon group may be an alkane group, an alkenyl group, an alkynyl group or an aromatic hydrocarbon group, and the substituent may be, for example, a halogen atom, a hydroxyl group, an acyloxy group, an amino group, a nitrile group or an alkoxy group. Etc., as examples of polymers, the silicone monomer can be, for example, diphenyldimethoxysilane, methyl orthosilicate, ethyl orthosilicate, diethylaminomethyltriethoxy Silane, diethylenetriaminopropyltrimethoxysilane, 1,1,1-trimethyl-N-2-propallylaminosilane, bis[3-(trimethoxysilyl)propyl]ethylenediamine , pentamethyldisiloxane, hexamethyldisiloxane, hexamethoxydisiloxane, hexaphenyldisiloxane, vinylpentamethyldisiloxane, 1-vinyl-1133- Tetramethyldisiloxane, 1,3-octyltetramethyldisiloxane, 1,1,3,3-tetramethyl-1,3-diphenyldisiloxane, 1,1, 3,3-tetramethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-bis(chloromethyl)tetramethyldisiloxane, 1,3-di Chlorotetramethyldisiloxane, 1,3-bis(4-hydroxybutyl)tetramethyldisiloxane, 1,3-bis(3-cyanopropyl)tetramethyldisiloxane, 1 ,3-Dimethyltetravinyldisiloxane, 13-dimethoxy-1133-tetramethyldisiloxane, 1,1,1,3,3,5,5-heptamethyltrisiloxane Oxane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane, 1 ,1,3,3,5,5-hexamethyltrisiloxane, 3-[[dimethyl(vinyl)silyl]oxy]-1,1,5,5-tetramethyl-3- Phenyl-1,5-divinyltrisiloxane, 1,5-dichloro-1,1,3,3,5,5-hexamethyltrisiloxane, octamethyltrisiloxane, Decamethyltetrasiloxane, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, 1,1,3,3,5,5,7,7-octamethyl Tetrasiloxane, 1,7-dichloro-1,1,3,3,5,5,7,7-octamethyltetrasiloxane, dodecamethylpentasiloxane, decamethyldisiloxane Hydrogen pentasiloxane, tetradecamethylhexasiloxane, 1,1,3,3,5,5,7,7,9,9,11,11-dodecamethylhexasiloxane, hexadecan Alkyl heptasiloxane, 1,1,3,3,5,5,7,7,9,9,11,11,13,13-tetradecamethylheptasiloxane, 1,1,3, 3,5,5,7,7,9,9,11,11,13,13,15,15-hexadecamethyloctasiloxane, polydimethylsiloxane, polymethylhydrogensiloxane , polydimethylsiloxane hydride-terminated, polyphenylmethylsiloxane, vinyl-terminated dimethylpolysiloxane, phenyltris(trimethylsiloxane)silane, vinyltris (Trimethylsiloxane)silane, Methyltris(trimethylsiloxane)silane, Ethyltris(trimethylsiloxane)silane, 1,1,1,3,5,7 ,7,7-octamethyl-3,5-bis(trimethylsiloxy)tetrasiloxane, 1,3-diphenyl-1,3-bis(trimethylsiloxy)disiloxane Oxane, allyl tris(trimethylsiloxy)silane, tetrakis(trimethylsiloxy)silane, (3-chloropropyl)tris(trimethylsiloxy)silane, methacryloyl Oxypropyl tris(trimethylsiloxane)silane, hexamethylcyclotrisiloxane, hexaethylcyclotrisiloxane, hexaphenylcyclotrisiloxane, hexaethylcyclotrisiloxane , 2,4,6-triethyl-2,4,6-trimethylcyclotrisiloxane, 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane , 2,4,6-trimethylcyclotrisiloxane, trimethyl-1,3,5-triphenylcyclotrisiloxane, 2,4,6-trivinyl-2,4,6 -Trimethylcyclotrisiloxane, octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, 2,2,4,4-tetramethyl-6,6,8,8-tetraphenyl cyclotetrasiloxane, decamethylcyclopentasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 1,3,5 ,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane Methylcyclotetrasiloxane, 2,4,6,8-tetramethyl-2-[3-(oxiranylmethoxy)propyl]cyclotetrasiloxane, 2,4-diene Base-2,4,6,6,8,8-hexamethylcyclotetrasiloxane, pentamethylpentavinylcyclopentasiloxane, 2,4,6,8,10-pentamethylcyclopentasiloxane Siloxane, dodecamethylcyclohexasiloxane, hexamethylhexavinylcyclohexasiloxane, hexamethylcyclooctasiloxane or octadecamethylcyclononasiloxane, among others.

The preparation method of the silicone hydrophobic film layer according to the specific embodiment of the present invention, in some specific embodiments, takes into account both wear resistance and hydrophobicity, and the R ₁ , R ₂ , R ₃ , R ₅ and R ₆ are respectively independent is selected from methyl or ethyl, especially methyl, the R ₄ is methyl, ethyl or trimethylsilyl, especially methyl or trimethylsilyl, and the n is 2-10 is an integer, and the siloxane monomer can be, for example, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylsiloxane, Hexasiloxane, hexamethylcyclotrisiloxane, hexaethylcyclotrisiloxane, octamethylcyclotetrasiloxane, octaethylcyclotetrasiloxane, decamethylcyclopentasiloxane Or dodecamethylcyclohexasiloxane and so on.

The preparation method of the silicone hydrophobic film layer according to the specific embodiment of the present invention. In some specific embodiments, considering that the silicone hydrophobic film layer has better wear resistance, the silicone monomer It includes siloxane monomer one and siloxane monomer two, wherein the siloxane monomer one has one unsaturated double bond, and the siloxane monomer two has at least two unsaturated double bonds. Further, in some specific embodiments, the siloxane monomer has a structure shown in the following formula (3),

In formula (3), R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are independently selected from hydrogen atoms or C ₁ -C ₄ hydrocarbon group, at least one of R ₁₀ , R ₁₁ and R ₁₂ is not a hydrogen atom, at least one of R ₁₃ , R ₁₄ and R ₁₅ is not a hydrogen atom, at least one of R ₁₆ , R ₁₇ and R ₁₈ is not a hydrogen atom. One is not a hydrogen atom, and p is an integer from 1 to 10. Further, in some specific embodiments, the R ₇ , R ₈ and R ₉ are each independently selected from a hydrogen atom or a methyl group, and the R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are each independently selected from methyl or ethyl. Further, in some specific embodiments, the siloxane monomer is methacryloyloxypropyl tris(trimethyl (siloxanyl)silane, further, in some specific embodiments, the siloxane monomer two has the structure shown in the following formula (2),

The R ₅ is a C ₁ -C ₄ alkenyl group, the R ₆ is a C ₁ -C ₄ alkane group, and further, in some specific embodiments, the siloxane monomer 2 is 1,3, 5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane. In some specific embodiments of the present invention, the molar ratio of the siloxane monomer one to the siloxane monomer two is 1:10-10:1. Specific examples can be 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 so on.

In the preparation method of the silicone hydrophobic film layer according to the specific embodiment of the present invention, a gauze is arranged between the monomer steam air inlet and the base material. Due to the diversion effect of the gauze, the monomer steam airflow entering the inside of the gauze is The distribution is more uniform, so that the surface of the substrate is in uniform contact with the siloxane monomer vapor as the coating material. In some specific embodiments, the gauze is arranged by directly wrapping the gauze around the substrate support. In some specific embodiments, the mesh size of the gauze is 10-500 mesh, specifically 10 mesh, 20 mesh, 30 mesh, 50 mesh, 100 mesh, 150 mesh, 200 mesh, 250 mesh, 300 mesh mesh, 350 mesh, 400 mesh, 450 mesh or 500 mesh, etc. The specific mesh size can be adjusted according to the specific type of siloxane monomer.

In the preparation method of the silicone hydrophobic film layer according to the specific embodiment of the present invention, in order to facilitate the silicone monomer vapor to be more evenly dispersed through the gauze and reach the surface of the substrate at different positions, the gauze is used to control the silicone monomer. The body vapor is guided, and the substrate rotates in the reaction chamber. In some embodiments, a bracket is provided in the reaction chamber, a support is provided on the bracket, and the substrate is placed on the support. The rotation of the bracket around the central axis of the bracket and the rotation of the support member around the central axis of the support drive the substrate to rotate in the reaction chamber. In some embodiments, the support member surrounds the The brackets are arranged on more than one layer, and more than one bracket is arranged on each layer. For example, the supports are arranged on 3-5 layers around the bracket, and 3-10 brackets are arranged on each layer. The base material is placed on the supports. The bracket rotates around the central axis of the bracket to form a revolution, and the support member rotates around the central axis of the support member to form an autorotation to form a planetary rotation. That is to say, all the objects placed on the support member form a planetary rotation. The substrate both rotates and revolves in the reaction chamber to provide more consistent coating conditions for all substrates, thereby ensuring that all substrates obtain uniform and consistent film layers to meet industrial batch requirements. production requirements.

In the preparation method of the silicone hydrophobic film layer according to the specific embodiment of the present invention, in some specific embodiments, the rotating speed of the stent is 1-10 rpm, specifically, it can be 1 rpm, 2 rpm /min, 3 revolutions/min, 4 revolutions/min, 6 revolutions/min, 7 revolutions/min, 9 revolutions/min or 10 revolutions/min, etc., the rotation speed of the support member is 1-10 revolutions/min, Specific examples include 1 revolution/min, 2 revolutions/min, 3 revolutions/min, 4 revolutions/min, 6 revolutions/min, 7 revolutions/min, 9 revolutions/min or 10 revolutions/min, etc.

The preparation method of the silicone hydrophobic film layer according to the specific embodiment of the present invention. In some specific embodiments, the water contact angle of the silicone hydrophobic film layer is greater than 100°. Specifically, it can be 100°, 101 °, 102°, 103°, 104°, 105°, 106°, 107°, 108°, 109°, 110°, 111°, 112°, 113°, 114°, 115°, 116°, 117°, 118°, 119°, 120°, 125°, 130°, 135°, 140°, 145° or 150° etc.

The preparation method of the silicone hydrophobic film layer according to the specific embodiment of the present invention. In some specific embodiments, the thickness of the film layer is 10-100nm. Specific examples can be 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm and so on.

The preparation method of the silicone hydrophobic film layer in the specific embodiment of the present invention. In some specific embodiments, in order to further improve the binding force of the silicone hydrophobic film layer, in some specific embodiments, in the coating The substrate is pretreated by continuous plasma beforehand. The specific pretreatment method is, for example, vacuuming to 10-200 mTorr, and passing in one or more mixed gases among He, Ar, and _O2 . Turn on plasma discharge to pretreat the substrate, or use heat, oxygen or high-energy radiation, etc.

The preparation method of the silicone hydrophobic film layer according to the specific embodiment of the present invention. In some specific implementations, pulse plasma discharge is used for the silicone monomer. In some specific implementations, the silicone monomer is treated with The oxyalkane monomer adopts continuous plasma discharge.

The preparation method of the silicone hydrophobic film layer according to the specific embodiment of the present invention. In some specific embodiments, the silicone monomer flow rate is 50-3000ul/min. For example, it can be 50ul/min, 100ul/min. min, 200ul/min, 300ul/min, 400ul/min, 500ul/min, 1000ul/min, 1500ul/min, 2000ul/min, 2500ul/min or 3000ul/min, etc.; the temperature in the cavity is controlled at 20℃-80 ° C, for example, it can be 20 ° C, 30 ° C, 40 ° C, 50 ° C, 60 ° C, 70 ° C or 80 ° C, etc.; the monomer gasification temperature is 50 ° C - 180 ° C, for example, it can be 50 ° C, 60 ° C , 70℃, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃ or 180℃, etc., and the gasification occurs under vacuum conditions, so The pulsed plasma is generated by applying pulse voltage discharge, and the continuous plasma discharge is generated by applying continuous voltage discharge, wherein the power of the continuous or pulse discharge is 10W-600W, specifically, it can 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 600W etc.; the frequency of pulse discharge is 10Hz-500Hz, for example, it can be 10Hz, 20Hz, 25Hz, 30Hz, 35Hz, 40Hz, 45Hz, 50Hz, 55Hz, 60Hz, 70Hz, 80Hz, 90Hz, 100Hz, 200Hz, 300Hz, 400Hz or 500Hz, etc.; the pulse duty cycle is 1% to 85%, specifically, it can be 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50 %, 55%, 60%, 65%, 70%, 75%, 80% or 85%, etc.; the plasma discharge time is 100s-36000s, specifically, it can be 100s, 500s, 1000s, 2000s, 3000s, 4000s, 5000s. , 6000s, 7000s, 8000s, 9000s, 10000s, 15000s, 20000s, 25000s, 30000s, 36000s and so on.

In the preparation method of the siloxane hydrophobic film layer according to the specific embodiment of the present invention, in some specific implementations, the plasma discharge method can be various existing discharge methods, specifically, for example, electrodeless discharge (such as radio frequency inductive coupling discharge , microwave discharge), single-electrode discharge (such as corona discharge, plasma jet formed by unipolar discharge), double-electrode discharge (such as dielectric barrier discharge, exposed electrode radio frequency glow discharge) and multi-electrode discharge (such as floating electrode as the discharge of the third electrode).

In the preparation method of the silicone hydrophobic film layer according to the specific embodiment of the present invention, in some specific embodiments, the substrate is various plastics, fabrics, glass, electrical components or optical instruments, etc. Specifically, the electrical component may be a printed circuit board (PCB), electronic product or electronic assembly semi-finished product, etc. In some embodiments, the substrate is an electronic or electrical component. As a specific non-limiting example, when the substrate is an electronic product, it can be a mobile phone, tablet computer, keyboard, e-reader, Wearable devices, monitors, headphones, USB data cables, USB interfaces, sound-transparent mesh, earmuffs or headbands, etc. The substrate can also be any suitable electrical component of an electrical component. Specifically, the electrical component can be a resistor, a capacitor, a transistor, a diode, an amplifier, a relay, a transformer, a battery, a fuse, an integrated circuit, a switch. , LED, LED display, piezoelectric components, optoelectronic components or antennas or oscillators, etc.

Specific embodiments of the present invention also provide a silicone hydrophobic film layer. In some specific embodiments, the silicone hydrophobic film layer is prepared by the above-mentioned preparation method of a silicone hydrophobic film layer. get.

Specific embodiments of the present invention also provide a siloxane hydrophobic film layer. In some specific embodiments, the siloxane hydrophobic film layer is contacted with a substrate and includes siloxane monomer and siloxane. A plasma polymerization coating formed by the plasma of monomer two siloxane monomers, wherein said siloxane monomer one has one unsaturated double bond and said siloxane monomer two has at least two unsaturated double bonds. Double bond. The plasma polymerization coating formed by the plasma of the siloxane monomer one having one unsaturated double bond and the siloxane monomer two having at least two unsaturated double bonds has more excellent wear resistance. Further descriptions of the first siloxane monomer, the second siloxane monomer, the base material, etc. are as described above.

Specific embodiments of the present invention also provide a device, at least part of the surface of the device has the above-mentioned silicone hydrophobic film layer. In some specific embodiments, part or all of the surface of the device is only coated with Covered with the protective coating described above. In some specific embodiments, the device is an electrical component, an optical instrument, an electronic or electrical component, etc. as mentioned above.

The present invention will be further described below through specific examples.

Example

Test method description

Coated water tentacle: tested according to GB/T 30447-2013 standard.

Film thickness test: Use American Filmetrics F20-UV-Film Thickness Measuring Instrument for testing.

Friction resistance performance test: Conducted on a wear-resistant testing machine, the friction material is a dust-free cloth, and the water contact angle before and after 1,000 times of friction is tested under the conditions of 1N pressure and 50 cycles/min.

Example 1

Place the Si wafer and glass substrate in the plasma chamber, place the substrate on the support of the bracket, wrap the support with 20 mesh gauze, evacuate the chamber to 20 millitorr, and pass helium gas at a flow rate of 80 sccm , the cavity temperature is 30℃;

Keep the chamber pressure at 20 mTorr and the helium flow at 80 sccm. Turn on the rotation of the bracket and the support. The substrate will perform planetary motion. The rotation speed of the bracket is 1 rpm and the rotation speed of the support is 1.5 rpm. Turn on the plasma. The body is continuously discharged, the discharge power is 100W, the discharge is continued for 600s, and the substrate is pretreated;

Then, the monomer dodecamethylcyclohexasiloxane was vaporized at a vaporization temperature of 75°C and then introduced into the plasma chamber. The chamber pressure was maintained at 20 mTorr, the helium flow rate was maintained at 80 sccm, and the stent was maintained. Rotate the support member and turn on the radio frequency plasma discharge. The energy output mode of the radio frequency is pulse. Plasma chemical vapor deposition is performed on the surface of the substrate. The pulse duty cycle is 25%, the pulse frequency is 200Hz, and the pulse discharge power is 120W. The monomer The flow rate is 160μL/min, and the reaction time is 3600s;

After the coating is completed, fill the chamber with compressed air to return to normal pressure, take out the coated substrate Si sheet and glass, and test the film thickness of the Si sheet as shown in Table 1 below, and the friction resistance test of the glass as shown in Table 2 below.

Comparative example 1

Place the Si wafer and glass substrate in the plasma chamber, place the substrate on the support of the bracket, evacuate the chamber to 20 mTorr, pass helium gas, the flow rate is 80 sccm, and the chamber temperature is 30°C;

Keep the chamber pressure at 20 mTorr and the helium flow rate at 80 sccm. Turn on the plasma continuous discharge with a discharge power of 100W and a continuous discharge of 600s to pretreat the substrate;

Then, the monomer dodecamethylcyclohexasiloxane is vaporized at a vaporization temperature of 75°C and introduced into the plasma chamber. The chamber pressure is maintained at 20 mTorr, the helium flow rate is maintained at 80 sccm, and the radio frequency is turned on. Plasma discharge, the energy output mode of radio frequency is pulse, and plasma chemical vapor deposition is performed on the surface of the substrate. The pulse duty cycle is 25%, the pulse frequency is 200Hz, the pulse discharge power is 120W, and the monomer flow rate is 160 μL/min. The reaction Time is 3600s;

After the coating is completed, fill the chamber with compressed air to return to normal pressure, take out the coated substrate Si sheet and glass, and test the film thickness of the Si sheet as shown in Table 1 below, and the friction resistance test of the glass as shown in Table 2 below.

Example 2

Place the Si wafer and glass substrate in the plasma chamber, place the substrate on the support of the bracket, wrap the support with 30 mesh gauze, evacuate the chamber to 50 mTorr, pass helium gas, and the flow rate is 70 sccm , the cavity temperature is 40℃;

Keep the chamber pressure at 50 mTorr and the helium flow at 70 sccm. Start the rotation of the bracket and the support. The substrate will perform planetary motion. The rotation speed of the bracket is 2 rpm and the rotation speed of the support is 2.5 rpm. Turn on the plasma. The body is continuously discharged, the discharge power is 300W, the discharge is continued for 300s, and the substrate is pretreated;

Then, the monomer decamethyltetrasiloxane is vaporized at a vaporization temperature of 80°C and then introduced into the plasma chamber. Maintain the chamber pressure at 50 mTorr, the helium flow rate at 70 sccm, and the bracket and support. The component rotates to turn on the radio frequency plasma discharge. The energy output mode of the radio frequency is pulse. Plasma chemical vapor deposition is performed on the surface of the substrate. The pulse duty cycle is 25%, the pulse frequency is 100Hz, the pulse discharge power is 180W, and the monomer flow rate is 150μL/min, reaction time is 1800s;

After the coating is completed, fill the chamber with compressed air to return to normal pressure, take out the coated substrate Si sheet and glass, and test the film thickness of the Si sheet as shown in Table 1 below, and the friction resistance test of the glass as shown in Table 2 below.

Comparative example 2

Place the Si wafer and glass substrate in the plasma chamber, place the substrate on the support of the bracket, evacuate the chamber to 50 mTorr, pass helium gas, the flow rate is 70 sccm, and the chamber temperature is 40°C;

Keep the chamber pressure at 50 mTorr and the helium flow rate at 70 sccm. Start continuous plasma discharge with a discharge power of 300W and continuous discharge for 300 seconds to pretreat the substrate;

Then, the monomer decamethyltetrasiloxane is vaporized at a vaporization temperature of 80°C and introduced into the plasma chamber. The chamber pressure is maintained at 50 mTorr, the helium flow rate is maintained at 70 sccm, and the radio frequency plasma is turned on. The energy output mode of discharge and radio frequency is pulse, and plasma chemical vapor deposition is performed on the surface of the substrate. The pulse duty cycle is 25%, the pulse frequency is 100Hz, the pulse discharge power is 180W, the monomer flow rate is 150μL/min, and the reaction time is 1800s;

After the coating is completed, fill the chamber with compressed air to return to normal pressure, take out the coated substrate Si sheet and glass, and test the film thickness of the Si sheet as shown in Table 1 below, and the friction resistance test of the glass as shown in Table 2 below.

Example 3

Place the Si wafer and glass substrate in the plasma chamber, place the substrate on the support of the bracket, wrap the support with 50 mesh gauze, evacuate the chamber to 100 mTorr, introduce helium gas, and the flow rate is 50 sccm , the cavity temperature is 50℃;

Keep the chamber pressure at 100 mTorr and the helium flow at 50 sccm. Turn on the rotation of the bracket and the support. The substrate will perform planetary motion. The rotation speed of the bracket is 1 rpm and the rotation speed of the support is 1.5 rpm. Turn on the plasma. Body pulse discharge, pulse duty cycle 45%, pulse frequency 300Hz, discharge power 250W, continuous discharge for 600s, pretreatment of the substrate;

Then, the monomer methacryloxypropyltris(trimethylsiloxane)silane was vaporized at a vaporization temperature of 80°C and then introduced into the plasma chamber, maintaining the chamber pressure at 100 mTorr. Keep the helium flow rate at 50 sccm, keep the bracket and support rotating, turn on the radio frequency plasma discharge, the energy output mode of the radio frequency is pulse, and perform plasma chemical vapor deposition on the surface of the substrate, with a pulse duty cycle of 10% and a pulse frequency of 150Hz. , the pulse discharge power is 100W, the monomer flow rate is 200μL/min, and the reaction time is 1800s;

After the coating is completed, fill the chamber with compressed air to return to normal pressure, take out the coated substrate Si sheet and glass, and test the film thickness of the Si sheet as shown in Table 1 below, and the friction resistance test of the glass as shown in Table 2 below.

Comparative example 3

Place the Si sheet and glass substrate in the plasma chamber, place the substrate on the support of the bracket, evacuate the chamber to 100 mTorr, pass helium gas, the flow rate is 50 sccm, and the chamber temperature is 50°C;

Keep the chamber pressure at 100 mTorr, the helium flow rate at 50 sccm, turn on the plasma pulse discharge, the pulse duty cycle is 45%, the pulse frequency is 300Hz, the discharge power is 250W, and the discharge is continued for 600s to pretreat the substrate;

Then, the monomer methacryloxypropyltris(trimethylsiloxane)silane was vaporized at a vaporization temperature of 80°C and then introduced into the plasma chamber, maintaining the chamber pressure at 100 mTorr. Keep the helium flow rate at 50sccm, turn on the radio frequency plasma discharge, the energy output mode of the radio frequency is pulse, and perform plasma chemical vapor deposition on the surface of the substrate, with a pulse duty cycle of 10%, a pulse frequency of 150Hz, and a pulse discharge power of 100W. The monomer flow rate is 200 μL/min, and the reaction time is 1800 s;

After the coating is completed, fill the chamber with compressed air to return to normal pressure, take out the coated substrate Si sheet and glass, and test the film thickness of the Si sheet as shown in Table 1 below, and the friction resistance test of the glass as shown in Table 2 below.

Example 4

Place the glass substrate in the plasma chamber, place the substrate on the support of the bracket, wrap the support with 50 mesh gauze, evacuate the chamber to 100 mTorr, introduce helium gas, the flow rate is 50 sccm, and the chamber The temperature is 50℃;

Keep the chamber pressure at 100 mTorr and the helium flow at 50 sccm. Turn on the rotation of the bracket and the support. The substrate will perform planetary motion. The rotation speed of the bracket is 1 rpm and the rotation speed of the support is 1.5 rpm. Turn on the plasma. Body pulse discharge, pulse duty cycle 45%, pulse frequency 300Hz, discharge power 250W, continuous discharge for 600s, pretreatment of the substrate;

Then, the monomers methacryloxypropyl tris(trimethylsiloxanyl)silane and 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasilane were Oxane (mass ratio 2:1) is vaporized at a gasification temperature of 80°C and then introduced into the plasma chamber. Keep the chamber pressure at 100 mTorr, the helium flow rate at 50 sccm, and the bracket and support parts to rotate. Turn on the radio frequency plasma discharge. The energy output mode of the radio frequency is pulse. Plasma chemical vapor deposition is performed on the surface of the substrate. The pulse duty cycle is 10%, the pulse frequency is 150Hz, the pulse discharge power is 100W, and the monomer flow rate is 200 μL/min. , the reaction time is 1800s;

After the coating is completed, compressed air is filled in to restore the chamber to normal pressure, and the coated substrate glass is taken out. The friction resistance test of the glass is listed in Table 2 below.

Example 5

Place the glass substrate in the plasma chamber, place the substrate on the support of the bracket, wrap the support with 100 mesh gauze, evacuate the chamber to 50 mTorr, introduce helium gas, the flow rate is 200 sccm, and the chamber The temperature is 45℃;

Keep the chamber pressure at 50 mTorr and the helium flow at 200 sccm. Turn on the rotation of the bracket and the support. The substrate will perform planetary motion. The rotation speed of the bracket is 2 rpm and the rotation speed of the support is 2.5 rpm. Turn on the plasma. Volume pulse discharge, pulse duty cycle 45%, pulse frequency 300Hz, discharge power 500W, continuous discharge for 60s, pretreat the substrate;

Then, the monomer octamethylcyclotetrasiloxane is vaporized at a vaporization temperature of 80°C and introduced into the plasma chamber. The chamber pressure is maintained at 50 mTorr, the helium flow rate is maintained at 50 sccm, and the bracket and The support rotates to turn on the radio frequency plasma discharge. The energy output mode of the radio frequency is continuous discharge, and plasma chemical vapor deposition is performed on the surface of the substrate. The continuous discharge power is 50W, the monomer flow rate is 1000 μL/min, and the reaction time is 3600s. ;

After the coating is completed, compressed air is filled in to restore the chamber to normal pressure, and the coated substrate glass is taken out. The friction resistance test of the glass is listed in Table 2 below.

Table 1 Film thickness test results

A, B, and C in the table respectively represent the farthest to the closest position of the Si chip base material from the rotation axis of the support.

According to the film thickness test results of Examples 1-3 in the above table, it can be seen that in Examples 1, 2 and 3, the gauze is wrapped around the support member, and the bracket and the support member are rotated at the same time to drive the base material to rotate. The difference in coating thickness at different locations on the substrate surface was significantly improved compared to the results in Comparative Examples 1-3.

Table 2 Friction resistance test results

Water contact angle before friction/° Water contact angle after friction/° Example 1 109 82 Comparative example 1 110 81 Example 2 110 76 Comparative example 2 108 73 Example 3 105 75 Comparative example 3 105 73 Example 4 106 90 Example 5 105 78

According to the results in Table 2 above, compared to Comparative Examples 1-3, in Examples 1-3, the gauze is wrapped around the support member, and the support and support members are rotated at the same time to drive the base material to rotate, and the film layer is coated The water contact angle before rubbing is basically the same, and the water contact angle after rubbing is slightly higher, indicating that the process will not affect the hydrophobicity of the coating; in Example 4, compared with Example 3, 1, 3, 5, and 7 -Tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane is used in combination with methacryloxypropyl tris(trimethylsiloxane)silane to obtain better wear resistance.

Although the present invention is disclosed as above, the present invention is not limited thereto. Any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention should be subject to the scope defined by the claims.

Claims (24)

1. A method for preparing a silicone hydrophobic film layer, which is characterized by comprising the following steps: Place the substrate in the plasma reaction chamber; A gauze is provided between the monomer steam inlet and the substrate. The silicone monomer steam is introduced into the plasma reaction chamber through the steam inlet, and the plasma discharge is started. The substrate is reacting Rotating motion in the chamber, the monomer vapor passes through the gauze and is deposited by plasma chemical vapor deposition on the surface of the substrate to form the silicone hydrophobic film layer. 2. The method for preparing a siloxane hydrophobic film layer according to claim 1, wherein the siloxane monomer includes at least one structure represented by the following formula (1) or (2), In formula (1) or (2), R ₁ , R ₂ , R ₃ , R ₅ and R ₆ are independently selected from hydrogen atoms, C ₁ -C ₁₂ substituted or unsubstituted hydrocarbon groups, C ₁ -C ₁₂ A substituted or unsubstituted hydrocarbyloxy group, or a C ₁ -C ₁₂ substituted or unsubstituted hydrocarbyl siloxy group, at least one of R ₁ , R ₂ and R ₃ is not a hydrogen atom, and the R ₅ or R ₆ At least one of them is not a hydrogen atom, R ₄ is a C ₁ -C ₁₂ substituted or unsubstituted hydrocarbon group, or a C ₁ -C ₁₂ substituted or unsubstituted hydrocarbon group silyl group, n is an integer from 1 to 100, m is 3- An integer of 10. 3. The method for preparing a siloxane hydrophobic film layer according to claim 2, wherein R ₁ , R ₂ , R ₃ , R ₅ and R ₆ are independently selected from methyl or ethyl. group, R ₄ is methyl, ethyl or trimethylsilyl, and n is an integer from 2 to 10. 4. The method for preparing a siloxane hydrophobic film layer according to claim 2, wherein the siloxane monomer includes siloxane monomer one and siloxane monomer two, wherein the siloxane monomer Silicone monomer one has one unsaturated double bond, and siloxane monomer two has at least two unsaturated double bonds. 5. The method for preparing a siloxane hydrophobic film layer according to claim 4, wherein the siloxane monomer has a structure represented by the following formula (3), In formula (3), R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are independently selected from hydrogen atoms or C ₁ -C ₄ hydrocarbon group, at least one of R ₁₀ , R ₁₁ and R ₁₂ is not a hydrogen atom, at least one of R ₁₃ , R ₁₄ and R ₁₅ is not a hydrogen atom, at least one of R ₁₆ , R ₁₇ and R ₁₈ is not a hydrogen atom. One is not a hydrogen atom, and p is an integer from 1 to 10. 6. The method for preparing a siloxane hydrophobic film layer according to claim 5, wherein the R ₇ , R ₈ and R ₉ are independently selected from hydrogen atoms or methyl groups, and the R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are each independently selected from methyl or ethyl. 7. The method for preparing a siloxane hydrophobic film layer according to claim 6, wherein the siloxane monomer is methacryloyloxypropyltris(trimethylsiloxane) Silane. 8. The method for preparing a siloxane hydrophobic film layer according to claim 4, characterized in that the siloxane monomer 2 has a structure shown in formula (2), and the R ₅ is C ₁ -C ₄ alkenyl group, and R ₆ is a C ₁ -C ₄ alkyl group. 9. The method for preparing a siloxane hydrophobic film layer according to claim 8, wherein the second siloxane monomer is 1,3,5,7-tetravinyl-1,3,5 ,7-Tetramethylcyclotetrasiloxane. 10. The method for preparing a silicone hydrophobic film layer according to claim 1, wherein the flow rate of the silicone monomer vapor is 10-2000 ul/min. 11. The method for preparing a silicone hydrophobic film layer according to claim 1, wherein the mesh size of the gauze is 10-500 mesh. 12. The method for preparing a silicone hydrophobic film layer according to claim 1, characterized in that a bracket is provided in the reaction chamber, a support member is provided on the support member, and the base material is placed on the support member. On the reaction chamber, the base material is driven to rotate in the reaction chamber by the rotation of the bracket around the central axis of the bracket and the rotation of the support member around the central axis of the support member. 13. The method for preparing a silicone hydrophobic film layer according to claim 12, characterized in that the rotation speed of the bracket is 1-10 rpm, and the rotation speed of the support member is 1-10 rpm. /min. 14. The method for preparing a silicone hydrophobic film layer according to claim 1, wherein the water contact angle of the silicone hydrophobic film layer is greater than 100°. 15. The method for preparing a siloxane hydrophobic film layer according to claim 1, characterized in that, before the chemical vapor deposition, the vacuum is evacuated to 10-200 mTorr, and the gases He, Ar, and O are introduced. Use one or more of the mixed gases in ₂ to start plasma discharge to pretreat the substrate. 16. A silicone hydrophobic film layer, characterized in that the silicone hydrophobic film layer is prepared by the preparation method of a silicone hydrophobic film layer according to any one of claims 1-15 . 17. A device having the silicone hydrophobic film layer according to claim 16 on at least part of its surface. 18. A silicone hydrophobic film layer, characterized in that the silicone hydrophobic film layer is formed by contacting a substrate with a silicone monomer including silicone monomer one and silicone monomer two. The plasma polymerization coating is formed by plasma, wherein the siloxane monomer one has one unsaturated double bond, and the siloxane monomer two has at least two unsaturated double bonds. 19. The siloxane hydrophobic film layer according to claim 18, characterized in that the siloxane monomer has a structure represented by the following formula (3), In formula (3), R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are independently selected from hydrogen atoms or C ₁ -C ₄ hydrocarbon group, at least one of R ₁₀ , R ₁₁ and R ₁₂ is not a hydrogen atom, at least one of R ₁₃ , R ₁₄ and R ₁₅ is not a hydrogen atom, at least one of R ₁₆ , R ₁₇ and R ₁₈ is not a hydrogen atom. One is not a hydrogen atom, and p is an integer from 1 to 10. 20. The silicone hydrophobic film layer according to claim 19, wherein the R ₇ , R ₈ and R ₉ are independently selected from hydrogen atoms or methyl groups, and the R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are each independently selected from methyl or ethyl. 21. The silicone hydrophobic film layer according to claim 20, wherein the silicone monomer is methacryloyloxypropyltris(trimethylsiloxane)silane. 22. The silicone hydrophobic film layer according to claim 18, characterized in that the silicone monomer two has a structure represented by the following formula (2), The R ₅ is a C ₁ -C ₄ alkenyl group, and the R ₆ is a C ₁ -C ₄ alkane group. 23. The siloxane hydrophobic film layer according to claim 21, characterized in that the siloxane monomer 2 is 1,3,5,7-tetravinyl-1,3,5,7-tetramethyl cyclotetrasiloxane. 24. A device, at least part of the surface of the device has the silicone hydrophobic film layer according to any one of claims 18 to 23.