Waterproof membrane layer and preparation method, application and product thereof
阅读说明：本技术 防水膜层及其制备方法、应用和产品 (Waterproof membrane layer and preparation method, application and product thereof ) 是由 宗坚 康必显 于 2020-05-18 设计创作，主要内容包括：防水膜层及其制备方法、应用和产品,其中所述防水膜层以一种或者是多种具有通式(I)所示的化合物通过等离子化学气相沉积方法在一基材表面形成,<Image he="165" wi="650" file="DDA0002496194750000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中R<Sub>1</Sub>和R<Sub>2</Sub>分别独立地选自氢、烷基、卤素、卤代烷基或者是芳基,其中R<Sub>1</Sub>、R<Sub>2</Sub>、R<Sub>3</Sub>中的至少一个是卤素,其中R<Sub>4</Sub>是基团-C(O)O(CH<Sub>2</Sub>)<Sub>n</Sub>C<Sub>m</Sub>F<Sub>2m+1</Sub>；或者R<Sub>4</Sub>是基团-O-C(O)-(CH<Sub>2</Sub>)<Sub>i</Sub>C<Sub>m</Sub>F<Sub>2m+1</Sub>；或者是R<Sub>4</Sub>是基团-(CH<Sub>2</Sub>)<Sub>x</Sub>C<Sub>m</Sub>F<Sub>2m+1</Sub>,其中n、i或者x分别是1～8的整数,m是1～12的整数。(A waterproof film layer, a preparation method, application and a product thereof, wherein the waterproof film layer is formed on the surface of a substrate by one or more compounds shown in a general formula (I) through a plasma chemical vapor deposition method, wherein R is 1 And R 2 Each independently selected from hydrogen, alkyl, halogen, haloalkyl or aryl, wherein R is 1 、R 2 、R 3 Is halogen, wherein R is 4 Is a group-C (O) O (CH) 2 ) n C m F 2m+1 (ii) a Or R 4 Is a group-O-C (O))‑(CH 2 ) i C m F 2m+1 (ii) a Or is R 4 Is a group- (CH) 2 ) x C m F 2m+1 Wherein n, i or x are integers of 1-8, and m is an integer of 1-12.)
1. A waterproof film layer, which is characterized in that one or more compounds shown in a general formula (I) are formed on the surface of a substrate by a plasma chemical vapor deposition method,
wherein R is1And R2Each independently selected from hydrogen, alkyl, halogen, haloalkyl or aryl, wherein R is1、R2、R3Is halogen, wherein R is4Is a group-C (O) O (CH)2)nCmF2m+1(ii) a Or R4Is a group-O-C (O) - (CH)2)iCmF2m+1(ii) a Or is R4Is a group- (CH)2)xCmF2m+1Wherein n, i or x are integers of 1-8, and m is an integer of 1-12.
2. The waterproofing membrane layer according to claim 1, wherein R3Is a halogen.
3. The waterproofing membrane layer according to claim 1 or 2 wherein the group-CmF2m+1Is a linear perfluoroalkyl group.
4. The waterproofing membrane layer according to claim 1 or 2 wherein m is no greater than 6.
5. The waterproofing membrane layer according to claim 1 or 2 wherein R1Is hydrogen.
6. The waterproofing membrane layer according to claim 1 or 2 wherein R2Is hydrogen.
7. The waterproof film layer according to claim 1 or 2, wherein n, i or x is 1-2.
8. A product having a water repellent film layer, characterized in that the product is provided with a water repellent film layer, wherein the water repellent film layer is formed on the surface of the product by a plasma chemical vapor deposition method using one or more compounds having the general formula (I),
wherein R is1And R2Each independently selected from hydrogen, alkyl, halogen, haloalkyl or aryl, wherein R is1、R2、R3Is halogen, wherein R is4Is a group-C (O) O (CH)2)nCmF2m+1(ii) a Or R4Is a group-O-C (O) - (CH)2)iCmF2m+1(ii) a Or is R4Is a group- (CH)2)xCmF2m+1Wherein n, i or x are integers of 1-8, and m is an integer of 1-12.
9. The product of claim 8, wherein the product is selected from one or more of a combination electronic product, a silk product, a metal product, a glass product, a ceramic product.
10. The product of claim 8 or 9, wherein m is no greater than 6.
11. The preparation method of the waterproof film layer is characterized by comprising the following steps: introducing one or more compounds shown in the general formula (I) into a reaction chamber of a plasma device as reaction raw materials, carrying out plasma enhanced chemical vapor deposition on the surface of a substrate in the plasma device to form a waterproof film layer,
wherein R is1And R2Each independently selected from hydrogen, alkyl, halogen, haloalkyl or aryl, wherein R is1、R2、R3Is halogen, wherein R is4Is a group-C (O) O (CH)2)nCmF2m+1(ii) a Or R4Is a group-O-C (O) - (CH)2)iCmF2m+1(ii) a Or is R4Is a group- (CH)2)xCmF2m+1Wherein n, i or x are integers of 1-8, and m is an integer of 1-12.
12. The method of manufacturing of claim 11, wherein the method of manufacturing further comprises the steps of: before the reaction raw materials are introduced, a plasma source gas is introduced for activating the chemical deposition reaction of the reaction raw materials.
13. The method of claim 12, wherein the plasma source gas is selected from one or both of a combination of an inert gas and a fluorocarbon gas.
14. The method according to claim 12, wherein in the above method, the reaction raw material further comprises a crosslinking agent, wherein the crosslinking agent is a multifunctional compound.
Technical Field
The invention relates to a surface modified film layer, in particular to a waterproof film layer formed by a plasma enhanced chemical vapor deposition method, a preparation method, application and a product thereof.
Background
It is a common technique to modify the surface of a substrate by forming a film layer on the surface of the substrate, for example, the film layer can improve the conductivity, oil resistance, or water resistance of the surface of the substrate.
Plasma Chemical Vapor Deposition (PCVD) has been widely used to deposit a polymer film on a substrate surface, wherein plasma is used to activate a reactive gas and promote the reactive gas to perform a chemical reaction on the substrate surface or a near-surface space to form a solid film.
The low polarizability and strong electronegativity of fluorine atoms in the fluorocarbon material endow fluorocarbon polymers with a plurality of unique properties, such as high hydrophobicity and oleophobicity and chemical reagent corrosion resistance, so that the fluorocarbon material is widely applied to surface modification in the fields of building coatings, textile industry and military industry.
However, plasma polymerization of satisfactory waterproof fluorocarbons is not so easy to achieve, and a class of unsaturated fluorocarbons prepared by plasma chemical vapor deposition techniques is reported in patent CN1190545, and the number of perfluoroalkyl carbon atoms in this series of compounds may be 6-12. In combination with other studies, it is known that the hydrophobicity of fluorocarbon compounds is closely related to the length of their perfluorocarbon chains. The waterproof fluorocarbon compound widely used at present is a fluorocarbon material with perfluoroalkyl group in the compound and the carbon atom number of more than 8. One reason for this is that when the number of carbon atoms of the perfluoroalkyl group in the fluorocarbon compound is 8 or less, for example, 6, the water-repellent property is significantly reduced, and it is difficult to meet the requirements of practical use. Patent document CN102471405B also discloses that when the number of carbons of the monomer perfluoroalkyl group in the fluorocarbon polymer is 6 or less, the hydrophobicity and oleophobicity are significantly reduced. This is considered to be due to the fact that the perfluoroalkyl group having 6 or less carbon atoms cannot form a crystal structure such as one having 8 or more carbon atoms.
Based on the research on such unsaturated fluorocarbons disclosed in patent CN1190545, it was found that when the number of carbon atoms in the fluorocarbon is 6, the waterproof performance is significantly reduced, and the waterproof performance is not stable.
On the other hand, the use of a large amount of long-carbon-chain perfluoroalkyl groups tends to produce environmentally harmful and hardly degradable organic substances like PFOA, PFOS, etc. Since 2003, the USEPA proposed that exposure to PFOA and its salts would lead to adverse effects on the health of the human body, and that PFOA was also banned under the influence of europe in the united states under the general safety standards (food-contact materials and substances resolution) imposed by the eu 2004/1935/EC directive; on 14.6.2017, the european union published (EU)2017/1000 in its official gazette, new REACH regulation annex XVII 68 on the restriction of perfluorooctanoic acid (PFOA), and officially incorporated PFOA, its salts and related substances into the REACH regulation list. PFOS was defined as a substance that persists in the environment, has biological storage, and is harmful to humans as early as 2002, 12 months, at the 34 th joint council of chemical council at OECD. These regulations create technical challenges to achieve good nano-protective coatings.
Therefore, it is necessary to develop a novel fluorocarbon material capable of forming a film on the surface of a substrate by a plasma chemical vapor deposition technique, and particularly, a fluorocarbon material which can maintain stable water-repellent properties even when the number of carbon atoms of a perfluoroalkyl group is not more than 8.
Disclosure of Invention
One advantage of the present invention is to provide a waterproof film layer, a method for preparing the same, and a product thereof, wherein the waterproof film layer is prepared from a fluorocarbon material by a plasma chemical vapor deposition technique and has good waterproof properties.
Another advantage of the present invention is to provide a waterproof film, a method for preparing the same, and a product thereof, wherein the waterproof film can improve the defect that the hydrophobic property of the film deposited when the number of carbon atoms of perfluoroalkyl group of fluorocarbon material is less than 8 is poor.
Another advantage of the present invention is to provide a waterproof film, a method for preparing the same, and a product thereof, wherein when the number of carbon atoms of perfluoroalkyl group of fluorocarbon material is 6 or less, the waterproof performance of the waterproof film is stable.
Another advantage of the present invention is to provide a waterproof film, a method for preparing the same, and a product thereof, wherein when the number of carbon atoms of perfluoroalkyl group of fluorocarbon material is 6 or less, the obtained static contact angle of the waterproof film is more than 110 °.
Another advantage of the present invention is to provide a waterproof film, a method for preparing the same, and a product thereof, wherein one or more fluorocarbon materials can be used as a reaction raw material gas, and deposited on the surface of a substrate by a plasma chemical vapor deposition technique to form the waterproof film.
Another advantage of the present invention is to provide a waterproof film, a method for preparing the same, and a product thereof, wherein the waterproof film can be deposited on various types of substrates, such as circuit boards, mobile phones, televisions, etc.
According to another aspect of the present invention, there is provided a product having a waterproof film layer, the product being provided with a waterproof film layer, wherein the waterproof film layer is formed on the surface of the product by a plasma chemical vapor deposition method using one or more compounds having the general formula (I),
wherein R is1And R2Each independently selected from hydrogen, alkyl, halogen, haloalkyl or aryl, wherein R is1、R2、R3Is halogen, wherein R is4Is a group-C (O) O (CH)2)nCmF2m+1(ii) a Or R4Is a group-O-C (O) - (CH)2)iCmF2m+1(ii) a Or is R4Is a group- (CH)2)xCmF2m+1Wherein n, i or x are integers of 1-8, and m is an integer of 1-12.
According to at least one embodiment of the invention, the product is selected from one or more of a combination electronic product, a silk fabric, a metal product, a glass product, a ceramic product.
According to at least one embodiment of the invention, m is not greater than 6.
According to another aspect of the present invention, there is provided a method for preparing a waterproof film layer, comprising the steps of: introducing one or more compounds shown in the general formula (I) into a reaction chamber of a plasma device as reaction raw materials, carrying out plasma enhanced chemical vapor deposition on the surface of a substrate in the plasma device to form a waterproof film layer,
wherein R is1And R2Each independently selected from hydrogen, alkyl, halogen, haloalkyl or aryl, wherein R is1、R2、R3Is halogen, wherein R is4Is a group-C (O) O (CH)2)nCmF2m+1(ii) a Or R4Is a group-O-C (O) - (CH)2)iCmF2m+1(ii) a Or is R4Is a group- (CH)2)xCmF2m+1Wherein n, i or x are integers of 1-8, and m is an integer of 1-12.
According to at least one embodiment of the invention, the method comprises the following steps: before the reaction raw materials are introduced, a plasma source gas is introduced for activating the chemical deposition reaction of the reaction raw materials.
According to at least one embodiment of the invention, the plasma source gas is selected from: one or more of inert gas and fluorocarbon gas.
According to at least one embodiment of the present invention, in the above method, the reaction raw material further includes a crosslinking agent, wherein the crosslinking agent is a multifunctional compound.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art. The basic principles of the invention, as defined in the following description, may be applied to other embodiments, variations, modifications, equivalents, and other technical solutions without departing from the spirit and scope of the invention.
It will be understood by those skilled in the art that in the present disclosure, the terms "halo" or "halogen" refer to fluoro, chloro, bromo, and iodo. The term "hydrocarbon" includes alkyl, alkenyl or aryl groups. The term "aryl" refers to an aromatic cyclic group such as phenyl or naphthyl, in particular phenyl. The term "alkyl" refers to a straight or branched chain of carbon atoms, suitably up to 20 carbon atoms in length. The term "alkenyl" refers to a straight or branched chain of unsaturation, suitably having from 2 to 20 carbon atoms.
It is understood that the terms "a" and "an" should be interpreted as meaning that a number of one element or element is one in one embodiment, while a number of other elements is one in another embodiment, and the terms "a" and "an" should not be interpreted as limiting the number.
The invention provides a waterproof film layer, a preparation method, application and a product thereof, wherein the waterproof film layer contains carbon, hydrogen and halogen. Optionally, the water repellent membrane layer contains carbon, hydrogen and fluorine. Optionally, the water repellent membrane layer contains carbon, hydrogen, fluorine and oxygen. The waterproof membrane layer has good hydrophobicity or lyophobicity. In other words, when the waterproof film is attached to a surface of a substrate, the waterproof film can provide good waterproof property to the surface of the substrate to prevent damage from water or other liquid.
The present invention provides products having a waterproof film layer, which in some examples of the invention may be, but is not limited to, electronic products, silks, woven bags, metal surfaces, glass products, or ceramic products.
When the product is an electronic device, the product may be, but is not limited to, a portable device, such as a keyboard, and the keyboard may become a waterproof keyboard by being coated with the waterproof coating. The product may be, but is not limited to, an LED display screen, a smart fingerprint lock, a hearing aid, a bluetooth headset, a sensor adapted to work in a liquid environment or often meet with water, a mobile phone, a notebook, a PSP, etc. electronic equipment that may meet with water in a work environment.
Further, when water adheres to the waterproofing membrane layer, the static contact angle of water is greater than 110 °. The static contact angle may be greater than 120, or 110 to 115, or 115 to 120.
The waterproof film layer is a nano film layer, and the thickness of the waterproof film layer can be made to be thin so as to be suitable for precise electronic equipment, for example, the thickness of the waterproof film layer can be 10 nm-20 nm, for example, 15 nm. The waterproof membrane layer can also be made thicker according to the requirement of a user, and optionally, the thickness range of the waterproof membrane layer can be, but is not limited to, 10 nm-2000 nm.
The waterproof film layer is formed on the surface of the substrate through a Plasma Enhanced Chemical Vapor Deposition (PECVD) process. That is, during the preparation process, the surface of the substrate is exposed to a chamber of a plasma enhanced chemical vapor deposition reaction apparatus, wherein plasma can be formed in the chamber, and the reactive material gas forms the waterproof film on the surface of the substrate through chemical deposition reaction.
Plasmas suitable for use in the provided preparation methods of the present invention include non-equilibrium plasmas such as those generated by radio frequency (Rf), microwave or Direct Current (DC). They may operate at atmospheric pressure, or at sub-atmospheric pressure. It is noted that the plasma source may be derived from a monomeric compound, i.e., no other gas is present, or another gas, such as an inert gas, is present, or is mixed with another gas. The unit for providing a plasma is referred to as a plasma source, wherein the description of the plasma source can be seen in the corresponding parts below. A plasma consisting only of the monomer compound can be obtained by first evacuating the reaction device as much as possible and then purging the reaction device with the monomer compound for a sufficient time to vent other gases within the reaction device.
Plasma Enhanced Chemical Vapor Deposition (PECVD) processes have many advantages over other existing deposition processes: (1) the method is a dry process, and the generated film is uniform and has no pinholes; (2) the plasma polymerization film has stable chemical and physical properties such as solvent resistance, chemical corrosion resistance, heat resistance, wear resistance and the like; (3) the plasma polymerization film has good adhesion with the base material; (4) a uniform film can be prepared on the surface of the base material with extremely irregular concave-convex parts; (5) the preparation temperature of the coating is low, and the coating can be carried out at normal temperature, so that damage to a temperature sensitive device is effectively avoided; (6) the plasma process can produce not only micron-sized coatings but also ultra-thin nanoscale coatings.
In the Plasma Enhanced Chemical Vapor Deposition (PECVD) process employed in the present invention, the plasma is generated by glow discharge, and the method of discharge may be, but is not limited to, microwave discharge, radio frequency discharge, ultraviolet, electric spark discharge, and the like.
Further, according to some embodiments of the present invention, during the formation of the waterproof film layer, the reaction raw material may be selected from monomer compounds having a general formula (I), wherein the general formula (I) is as follows:
wherein R is1、R2And R3Independently selected from hydrogen, alkyl, halogen, haloalkyl or aryl, wherein R is1、 R2And R3Is halogen, wherein R is4Is a group-C (O) O (CH)2)nCmF2m+1(ii) a Or R4Is a group-O-C (O) - (CH)2)iCmF2m+1(ii) a Or is R4Is a group- (CH)2)xCmF2m+1Wherein n, i or x are integers of 1-8, and m is an integer of 1-12. Alternatively, CmF2m+1The linear fluoroalkyl group may be a branched fluoroalkyl group, or may have a cyclic structure. Alternatively, m is less than 8, such as not greater than 6.
Further, when R is4In (C is a hydrogen atom) (- (CH)2)nAs functional groups-C (O) O-, -O-C (O) -and CmF2m+1The buffer segment between the two is controlled in a proper chain length range, and the fluorine content of the whole molecule is reduced due to too long chain length, which is not beneficial to improving the hydrophobic property. Optionally, n, i or x may take a value of 1 or 2.
When R of the monomer compound is4When the fluorinated alkyl group is used, in order to avoid the burden of PFOA and PFOS on the environment, the value of m may be selected to be an integer of 1-7.
According to some embodiments of the present invention, the monomer compound of formula (I) as a reaction raw material is implemented as a compound of formula (II) below,
wherein R is1Is halogen, wherein R4Is a group-C (O) O (CH)2)nCmF2m+1(ii) a Or R4Is a group-O-C (O) - (CH)2)iCmF2m+1(ii) a Or is R4Is a group- (CH)2)xCmF2m+1Wherein n, i or x are integers of 1-8, and m is an integer of 1-12. Alternatively, CmF2m+1The linear fluoroalkyl group may be a branched fluoroalkyl group, or may have a cyclic structure. Alternatively, m is less than 8, such as not greater than 6.
According to some embodiments of the present invention, the monomer compound of formula (I) as a reaction raw material is implemented as a compound of formula (III) below,
wherein R is3Is halogen, wherein R4Is a group-C (O) O (CH)2)nCmF2m+1(ii) a Or R4Is a group-O-C (O) - (CH)2)iCmF2m+1(ii) a Or is R4Is a group- (CH)2)xCmF2m+1Wherein n, i or x are integers of 1-8, and m is an integer of 1-12. Alternatively, CmF2m+1The linear fluoroalkyl group may be a branched fluoroalkyl group, or may have a cyclic structure. Alternatively, m is less than 8, such as not greater than 6.
Further, when R is4In (C is a hydrogen atom) (- (CH)2)nAs functional groups-C (O) O-, -O-C (O) -and CmF2m+1The buffer segment between the two is controlled in a proper chain length range, and the fluorine content of the whole molecule is reduced due to too long chain length, which is not beneficial to improving the hydrophobic property. Optionally, n, i or x may take a value of 1 or 2.
When R of the monomer compound is4When the fluorinated alkyl group is used, in order to avoid the burden of PFOA and PFOS on the environment, the value of m may be selected to be an integer of 1-7.
According to some embodiments of the present invention, the monomer compound of formula (I) as a reaction raw material is implemented as a compound of formula (IV),
According to some embodiments of the present invention, the monomer compound of formula (I) as a reaction raw material is implemented as a compound of formula (V) below,
wherein R is2And R3Independently selected from hydrogen, alkyl, halogen, haloalkyl or aryl, wherein R is2And R3Is halogen, wherein R is4Is a group-C (O) O (CH)2)nCmF2m+1(ii) a Or R4Is a group-O-C (O) - (CH)2)iCmF2m+1(ii) a Or is R4Is a group- (CH)2)xCmF2m+1Wherein n, i or x are integers of 1-8, and m is an integer of 1-12. Alternatively, CmF2m+1The linear fluoroalkyl group may be a branched fluoroalkyl group, or may have a cyclic structure. Alternatively, m is less than 8, such as not greater than 6.
Further, according to an embodiment of the present invention, in the forming of the waterproof film layer, the reactive raw material may be selected from one or more of the above monomer compounds, and in order to increase the degree of crosslinking of the waterproof film layer, a crosslinking agent may be further added, wherein the crosslinking agent is a compound having a multifunctional crosslinking structure. During plasma glow discharge, active groups with higher energy in the cross-linking agent are broken by low-temperature plasma to form active points, and the introduced additional active points are cross-linked and polymerized mutually in the plasma environment to form a compact network structure.
According to an embodiment of the present invention, the cross-linking agent may be a polyfunctional unsaturated hydrocarbon derivative, which may be selected from one or more of the group consisting of ethoxylated trimethylolpropane triacrylate, tripropylene glycol diacrylate, divinylbenzene, polyethylene glycol diacrylate, 1, 6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol divinyl ether, neopentyl glycol diacrylate.
Further, according to an embodiment of the present invention, the preparation process of the waterproof film layer may be: the method comprises the steps of preparing a waterproof film layer on the surface of a base material by utilizing a PECVD (plasma enhanced chemical vapor deposition) process, placing the base material in a reaction cavity of a vacuum or low-pressure reaction device, introducing reaction raw materials, generating plasma by utilizing glow discharge, and activating the reaction raw materials to perform chemical vapor deposition reaction on the surface of the base material.
According to an embodiment of the present invention, the method for preparing the waterproof film layer may include the steps of:
1) substrate preparation
Before the chemical vapor deposition of the substrate, the substrate is cleaned to remove dust, moisture or grease from the surface of the substrate. The substrate may be washed with an organic solvent such as acetone or isopropyl alcohol, and then placed in the reaction chamber of the reaction apparatus.
2) Preparing the waterproof film layer on the surface of the substrate by utilizing a PECVD technology
Continuously vacuumizing the reaction cavity of the reaction device, then vacuumizing the vacuum degree in the reaction cavity to 10-200 mTorr, and introducing a plasma source gas;
and introducing reaction raw materials until the vacuum degree is 30-300 mTorr, starting plasma discharge, performing chemical vapor deposition, and preparing the waterproof film layer on the surface of the substrate. The reaction raw material may be a monomer compound of the general formula (I) or a mixture of a monomer compound of the general formula (I) and a crosslinking agent.
When the reaction raw material is a mixture of the monomer compound with the general formula (I) and the cross-linking agent, the cross-linking agent accounts for 30-50% of the reaction raw material.
And then stopping plasma discharge, stopping introducing the reaction raw materials, continuously vacuumizing, introducing the atmosphere to normal pressure after keeping the vacuum degree of the reaction cavity at 10-200 mTorr for 1-5 minutes, and then taking out the substrate.
According to the embodiment of the invention, the substrate in the preparation method is a solid material, such as an electronic component or an electric component, and the waterproof film layer prepared on the surface of the substrate can be exposed to the environment of the international industrial waterproof grade standard IPX1-IPX8 for use.
According to the embodiment of the invention, the volume of the reaction cavity in the preparation method is 50-1000L, and the temperature of the reaction cavity is controlled at 30-60 ℃; and introducing inert gas or nitrogen at a flow rate of 5-300 sccm, wherein the inert gas is one of argon gas or helium gas, or a mixture of argon gas and helium gas.
According to the embodiment of the invention, the reaction raw materials are introduced into the preparation method through atomization and volatilization by a feeding pump, the reaction raw materials are introduced into the reaction cavity from 10 mTorr to 200 mTorr at low pressure, and the flow of the introduced reaction raw materials is 10-1000 muL/min.
According to an embodiment of the invention, the substrate is subjected to a bombardment pretreatment prior to the introduction of the reaction raw material.
According to the embodiment of the invention, in the preparation method, the power for starting plasma discharge is 2-500W, the duration discharge time is 600-.
According to the embodiment of the invention, in the preparation method, the energy output mode of the plasma radio frequency is controlled to be pulse or continuous output in the plasma radio frequency discharge process, and when the energy output mode of the plasma radio frequency is pulse output, the pulse width is 2 mus-1 ms, and the repetition frequency is 20Hz-10 kHz.
According to an embodiment of the present invention, in the preparation method, the plasma source may be a fluorocarbon gas. The plasma source forming the water repellent film layer has the structural formula: cxF2x+2Or CxF2xWherein x is 1, 2, 3. That is, the number of carbon atoms of the plasma source used is at most 3 and less than 4. In this way, one of the raw materials of the waterproof nanomembrane has a low carbon number, thereby reducing the formation of organic substances which are harmful to the environment and difficult to degrade. Preferably, the plasma source gas is selected from one of carbon tetrafluoride, tetrafluoroethylene, and hexafluoroethane.
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