CN111690306A - Waterproof film layer and preparation method and product thereof - Google Patents
Waterproof film layer and preparation method and product thereof Download PDFInfo
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- CN111690306A CN111690306A CN202010419177.0A CN202010419177A CN111690306A CN 111690306 A CN111690306 A CN 111690306A CN 202010419177 A CN202010419177 A CN 202010419177A CN 111690306 A CN111690306 A CN 111690306A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/62—Plasma-deposition of organic layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
- B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
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Abstract
A waterproof film layer, a preparation method 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 is1、R2And R3Independently selected from hydrogen, alkyl, halogen, haloalkyl or aryl, wherein R is1、R2And R3Is halogen, wherein R is4Is a group X-R5，R5Is alkyl or is a haloalkyl group and X is a bond; or X is a group-C (O) O (CH)2)nY-wherein n is an integer of 0 to 10 and Y is a bond or a sulfonamide group(ii) a Or X is a group-O-C (O) - (CH)2)iZ-, wherein i is an integer of 1 to 10, and Z is a bond or a sulfonamide group; or X is a group- (CH)2)xU-, wherein x is an integer of 1 to 10, and U is a bond or a sulfonamide group; or X is a group- (O)pR6(O)q(CH2)t-, wherein R6Is aryl optionally substituted with halogen.
Description
Technical Field
The invention relates to a surface modified film, in particular to a waterproof film formed by a plasma enhanced chemical vapor deposition method, a preparation method 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.
Another advantage of the present invention is to provide a waterproof film, a method for preparing the same, applications thereof, and products thereof, which reduce environmental pollution from the viewpoint of raw materials and make the waterproof film prepared from environmentally friendly raw materials have better hydrophobicity.
According to one aspect of the present invention, there is provided a waterproof film layer formed on a substrate surface by a plasma chemical vapor deposition method using one or more compounds represented by the general formula (I),
wherein R is1、R2And R3Independently selected from hydrogen, alkyl, halogen, haloalkyl or aryl, wherein R is1、R2And R3Is halogen, wherein R is4Is a group X-R5，R5Is alkyl or is a haloalkyl group and X is a bond; or X is a group-C (O) O (CH)2)nY-, wherein n is an integer of 0 to 10, and Y is a bond or a sulfonamide group; orIs X is a group-O-C (O) - (CH)2)iZ-, wherein i is an integer of 1 to 10, and Z is a bond or a sulfonamide group; or X is a group- (CH)2)xU-, wherein x is an integer of 1 to 10, and U is a bond or a sulfonamide group; or X is a group- (O)pR6(O)q(CH2)t-, wherein R6Is aryl optionally substituted with halogen, p is 0 or 1, q is 0 or 1 and t is 0 or an integer from 1 to 10, with the proviso that when q is 1, t is not 0.
According to one embodiment of the invention, the compound of formula (I) is a compound of formula (II),
wherein R is3Is halogen, R4Is a group-R5Or is a group-C (O) O (CH)2)nR5Or is a group-O-C (O) - (CH)2)iR5，R5Is a haloalkyl group.
According to one embodiment of the invention, R5Is a perhaloalkyl group.
According to one embodiment of the invention, n is an integer from 1 to 8.
According to one embodiment of the invention, R5Is of the general formula CmF2m+1A group of (1).
According to one embodiment of the invention, m is an integer from 1 to 8.
According to another aspect of the present invention, there is provided a product having a waterproof film layer, wherein the product is 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 represented by the general formula (I),
wherein R is1、R2And R3Independently selected from hydrogen, alkyl, halogen, haloalkyl or aryl, wherein R is1、R2And R3Is halogen, wherein R is4Is a group X-R5，R5Is alkyl or is a haloalkyl group and X is a bond; or X is a group-C (O) O (CH)2)nY-, wherein n is an integer of 0 to 10, and Y is a bond or a sulfonamide group; or X is a group-O-C (O) - (CH)2)iZ-, wherein i is an integer of 1 to 10, and Z is a bond or a sulfonamide group; or X is a group- (CH)2)xU-, wherein x is an integer of 1 to 10, and U is a bond or a sulfonamide group; or X is a group- (O)pR6(O)q(CH2)t-, wherein R6Is aryl optionally substituted with halogen, p is 0 or 1, q is 0 or 1 and t is 0 or an integer from 1 to 10, with the proviso that when q is 1, t is not 0.
According to an embodiment of the present invention, the product is one or more selected from a group consisting of a combination electronic product, a silk product, a metal product, a glass product, and a ceramic product.
According to another aspect of the present invention, there is provided a method for preparing a waterproof film, wherein the method comprises 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 is1、R2And R3Independently selected from hydrogen, alkyl, halogen, haloalkyl or aryl, wherein R is1、R2And R3Is halogen, wherein R is4Is a group X-R5，R5Is alkyl or is a haloalkyl group and X is a bond; or X isThe group-C (O) O (CH)2)nY-, wherein n is an integer of 0 to 10, and Y is a bond or a sulfonamide group; or X is a group-O-C (O) - (CH)2)iZ-, wherein i is an integer of 1 to 10, and Z is a bond or a sulfonamide group; or X is a group- (CH)2)xU-, wherein x is an integer of 1 to 10, and U is a bond or a sulfonamide group; or X is a group- (O)pR6(O)q(CH2)t-, wherein R6Is aryl optionally substituted with halogen, p is 0 or 1, q is 0 or 1 and t is 0 or an integer from 1 to 10, with the proviso that when q is 1, t is not 0.
According to an embodiment of the present invention, the method comprises the following steps: and firstly passing a plasma source gas between the two reaction raw materials for activating the chemical deposition reaction of the reaction raw materials.
According to an embodiment of the invention, the plasma source gas is selected from: one or two of inert gas and fluorocarbon gas.
According to an embodiment of the present invention, in the above method, the reaction raw material further includes a cross-linking agent, wherein the cross-linking 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 to 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 film layer. 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 membrane layer is a nano membrane layer which can be made thin to be suitable for precise electronic equipment, and the thickness of the waterproof membrane 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 reaction raw material forms the waterproof film layer 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 from a monomer compound, i.e., no other gas is present, or from another gas, such as an inert gas, or the monomer compound may be 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 the general formula (I). The structure of formula (I) is shown below:
wherein R is1、R2And R3Independently selected from hydrogen, alkyl, halogen, haloalkyl or aryl, wherein R is1、R2And R3Is halogen, wherein R is4Is a group X-R5，R5Is alkyl or is a haloalkyl group and X is a bond; or X is a group-C (O) O (CH)2)nY-, wherein n is an integer of 0 to 10, and Y is a bond or a sulfonamide group; or X is a group-O-C (O) - (CH)2)iZ-, wherein i is an integer of 1 to 10, and Z is a bond or a sulfonamide group; or X is a group- (CH)2)xU-, wherein x is an integer of 1 to 10, and U is a bond or a sulfonamide group; or X is a group- (O)pR6(O)q(CH2)t-, wherein R6Is aryl optionally substituted with halogen, p is 0 or 1, q is 0 or 1 and t is 0 or an integer from 1 to 10, with the proviso that when q is 1, t is not 0.
Further, when R is5When it is a haloalkyl group, R5May be a perhaloalkyl group. According to some embodiments of the invention, R5Is CmF2m+1And m may be an integer ranging from 1 to 13. Alternatively, R5May be a straight chain alkyl or a branched chainAn alkyl group. Alternatively, m is less than 8, such as not greater than 6.
Further, when X is a functional group, - (CH) in X2)nAs a buffer between the functional groups-C (O) O-, -O-C (O) -and Z or U, a chain length is suitably controlled, and too long a chain length lowers the fluorine content of the whole molecule, which is disadvantageous for improving the hydrophobic property. Optionally, n, i or x may take a value of 1 or 2.
When R of the monomer compound is5When 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 is3Is halogen, wherein R4Is a group X-R5，R5Is alkyl or is a haloalkyl group and X is a bond; or X is a group-C (O) O (CH)2)nY-, wherein n is an integer of 0 to 10, and Y is a bond or a sulfonamide group; or X is a group-O-C (O) - (CH)2)iZ-, wherein i is an integer of 1 to 10, and Z is a bond or a sulfonamide group; or X is a group- (CH)2)xU-, wherein x is an integer of 1 to 10, and U is a bond or a sulfonamide group; or X is a group- (O)pR6(O)q(CH2)t-, wherein R6Is aryl optionally substituted with halogen, p is 0 or 1, q is 0 or 1 and t is 0 or an integer from 1 to 10, with the proviso that when q is 1, t is not 0.
Further, when R is5When it is a haloalkyl group, R5May be embodied as a perhaloalkyl group. According to some embodiments of the invention, R5Is CmF2m+1And m may be an integer ranging from 1 to 13. Alternatively,m is not more than 6.
Further, when X is a functional group, - (CH) in X2)nAs a buffer between the functional groups-C (O) O-, -O-C (O) -and Z or U, a chain length is suitably controlled, and too long a chain length lowers the fluorine content of the whole molecule, which is disadvantageous for improving the hydrophobic property. Optionally, n, i or x may take a value of 1 or 2.
When R of the monomer compound is5When 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 (III) below,
wherein R is1Can be selected from hydrogen, alkyl, halogen, haloalkyl or haloaryl, R1Or is R4Is halogen, for example chlorine, wherein R4Is a group X-R5，R5Is alkyl or is a haloalkyl group and X is a bond; or X is a group-C (O) O (CH)2)nY-, wherein n is an integer of 0 to 10, and Y is a bond or a sulfonamide group; or X is a group-O-C (O) - (CH)2)iZ-, wherein i is an integer of 1 to 10, and Z is a bond or a sulfonamide group; or X is a group- (CH)2)xU-, wherein x is an integer of 1 to 10, and U is a bond or a sulfonamide group; or X is a group- (O)pR6(O)q(CH2)t-, wherein R6Is aryl optionally substituted with halogen, p is 0 or 1, q is 0 or 1 and t is 0 or an integer from 1 to 10, with the proviso that when q is 1, t is not 0.
Further, when R is5When it is a haloalkyl group, R5May be embodied as a perhaloalkyl group. According to some embodiments of the invention, R5Is CmF2m+1And m may be an integer ranging from 1 to 13. Optionally, m is 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 (IV),
wherein R is1Or is R2Each independently selected from hydrogen, alkyl, halogen, haloalkyl or aryl, and R1And/or R2Is halogen, wherein R4Is a group X-R5，R5Is alkyl or is a haloalkyl group and X is a bond; or X is a group-C (O) O (CH)2)nY-, wherein n is an integer of 0 to 10, and Y is a bond or a sulfonamide group; or X is a group-O-C (O) - (CH)2)iZ-, wherein i is an integer of 1 to 10, and Z is a bond or a sulfonamide group; or X is a group- (CH)2)xU-, wherein x is an integer of 1 to 10, and U is a bond or a sulfonamide group; or X is a group- (O)pR6(O)q(CH2)t-, wherein R6Is aryl optionally substituted with halogen, p is 0 or 1, q is 0 or 1 and t is 0 or an integer from 1 to 10, with the proviso that when q is 1, t is not 0.
Further, when R is5When it is a haloalkyl group, R5May be embodied as a perhaloalkyl group. According to some embodiments of the invention, R5Is CmF2m+1And m may be an integer ranging from 1 to 13. Optionally, m is 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 (V) below,
wherein R is2Or is R3Each independently selected from hydrogen, alkyl, halogen, haloAlkyl or aryl, and R2Or is R3At least one of (A) and (B) is halogen, and may be R2And R3Are all halogens, such as chlorine. R4Is a group X-R5，R5Is alkyl or is a haloalkyl group and X is a bond; or X is a group-C (O) O (CH)2)nY-, wherein n is an integer of 0 to 10, and Y is a bond or a sulfonamide group; or X is a group-O-C (O) - (CH)2)iZ-, wherein i is an integer of 1 to 10, and Z is a bond or a sulfonamide group; or X is a group- (CH)2)xU-, wherein x is an integer of 1 to 10, and U is a bond or a sulfonamide group; or X is a group- (O)pR6(O)q(CH2)t-, wherein R6Is aryl optionally substituted with halogen, p is 0 or 1, q is 0 or 1 and t is 0 or an integer from 1 to 10, with the proviso that when q is 1, t is not 0.
Further, when R is5When it is a haloalkyl group, R5May be embodied as a perhaloalkyl group. According to some embodiments of the invention, R5Is CmF2m+1And m may be an integer ranging from 1 to 13. Optionally, m is 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 reactive raw materials, generating plasma by utilizing glow discharge, and activating the reactive 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 of the general formula (I) and the crosslinking agent, the proportion of the crosslinking agent in the reaction raw material can be 30-50%.
And then stopping plasma discharge, stopping introducing the reaction raw materials, continuously vacuumizing, keeping the vacuum degree of the reaction cavity at 10-200 mTorr, introducing atmosphere to normal pressure after 1-5 minutes, and 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 chamber in the preparation method is 50-1000L, the temperature of the reaction chamber is controlled to be 30-60 ℃, the flow rate of introducing inert gas or nitrogen at DEG C is 5-300 sccm, and 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 rate 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, 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. OptionallyThe plasma source gas is selected from one of carbon tetrafluoride, tetrafluoroethylene and hexafluoroethane.
Example 1
A preparation method of a waterproof electric breakdown-resistant coating comprises the following steps:
(1) placing a substrate in the reaction cavity of the reaction device, continuously vacuumizing the reaction cavity, vacuumizing the vacuum degree in the reaction cavity to 10 mTorr, and introducing inert gas of a plasma source;
(2) introducing reaction raw materials to a vacuum degree of 30 mTorr, starting plasma discharge, performing chemical vapor deposition, and preparing the waterproof film layer on the surface of the base material; and
(3) stopping plasma discharge, stopping introducing the reaction raw materials, continuously vacuumizing, keeping the vacuum degree of the reaction cavity at 10 mTorr, introducing the atmosphere to normal pressure after 1min, for example, one atmosphere, and then taking out the substrate.
In step (1), the substrate is a solid material which is an electronic component-circuit board, and any interface of the substrate surface after the waterproof film layer is prepared can be exposed to the environment of the international industrial waterproof grade IPX1 for use.
In the step (1), the volume of the reaction chamber of the reaction device is 50L, the temperature of the reaction chamber is controlled to be 30 ℃, the flow rate of introducing inert gas at the temperature of 5sccm is 5sccm, and the inert gas is argon.
In the step (2), the reaction raw materials are atomized and volatilized by a feeding pump and are introduced into the reaction cavity from 10 mTorr at low pressure, and the flow rate of the reaction raw materials is 10 mu L/min. The reaction raw material comprises the following components:
in the step (2), bombardment pretreatment is carried out on the base material by glow discharge before fluorocarbon monomer steam is introduced.
In the step (2), the power of starting plasma discharge is 2W, the continuous discharge time is 7200 seconds, the plasma discharge mode is radio frequency discharge, the energy output mode of controlling plasma radio frequency in the plasma radio frequency discharge process is pulse output, when the energy output mode of plasma radio frequency is pulse output, the pulse width is 2 mus, and the repetition frequency is 20 Hz.
Example 2
The basic process steps of the present example are the same as those of example 1, and the different process parameters are as follows:
in the step (1), the vacuum degree in the reaction cavity is pumped to 40 mTorr, and inert gas is introduced.
In the step (1), the substrate is a solid material, the solid material is an electrical appliance part-television shell, and any interface of the substrate surface after the waterproof film layer is prepared can be exposed to the environment of the international industrial waterproof grade IPX3 for use.
In the step (1), the volume of the reaction device is 260L, the temperature of the reaction device is controlled at 40 ℃, the flow rate of introducing inert gas is 60sccm, and the inert gas is helium.
In the step (2), the reaction raw material is introduced to a vacuum degree of 80 mTorr, and plasma discharge is started.
And introducing reaction raw material steam, namely atomizing and volatilizing the reaction raw materials through a feed pump, into the reaction cavity from low pressure of 40 mTorr, wherein the flow of the introduced reaction raw materials is 90 mu L/min.
The reaction raw material components are as follows:
in the step (2), the power of starting plasma discharge is 25W, the continuous discharge time is 5800 seconds, the plasma discharge mode is radio frequency discharge, the energy output mode of controlling plasma radio frequency in the plasma radio frequency discharge process is pulse output, when the energy output mode of plasma radio frequency is pulse output, the pulse width is 0.1ms, and the repetition frequency is 400 Hz.
Example 3
The basic process steps of the present example are the same as those of example 1, and the different process parameters are as follows:
in the step (1), the vacuum degree in the reaction cavity is pumped to 100 mTorr, and fluorocarbon gas is introduced to be used as a plasma source gas.
In step (1), the substrate is a solid material, the solid material is an electronic component-mobile phone, and any interface of the substrate surface after the waterproof coating is prepared can be exposed to the environment of the international industrial waterproof grade standard IPX4 for use.
In the step (1), the volume of the reaction chamber is 380L, the temperature of the reaction chamber is controlled at 45 ℃, the flow of fluorocarbon gas introduced at the temperature of 130sccm is 130sccm, and the fluorocarbon gas is tetrafluoroethane.
In the step (2), the reaction material was introduced to a vacuum of 130 mTorr, and the plasma discharge was started.
The reaction raw materials are atomized and volatilized by a feeding pump and are introduced into the reaction cavity at low pressure of 100 millitorr, and the flow of the introduced reaction raw materials is 180 mu L/min.
The reaction raw materials are as follows:
in the step (2), the power of starting plasma discharge is 100W, the continuous discharge time is 4500 seconds, the plasma discharge mode is radio frequency discharge, the energy output mode of controlling plasma radio frequency in the plasma radio frequency discharge process is pulse output, when the energy output mode of plasma radio frequency is pulse output, the pulse width is 1ms, and the repetition frequency is 10 kHz.
In the step (3), the vacuum degree of the reaction cavity is kept at 130 mTorr, and the atmosphere is introduced to one atmosphere after 3 min.
Example 4
The basic process steps of the present example are the same as those of example 1, and the different process parameters are as follows:
in the step (1), the vacuum degree in the reaction cavity is pumped to 150 mTorr, and nitrogen is introduced, wherein
The substrate is a solid material which is an electrical appliance part, and any interface of the substrate surface after the waterproof coating is prepared can be exposed to the environment of the international industrial waterproof grade standard IPX6 for use.
In the step (1), the volume of the reaction chamber is 560L, the temperature of the reaction chamber is controlled at 50 ℃, and the flow rate of introducing nitrogen as a plasma source is 220 sccm.
In the step (2), the reaction material is introduced to a vacuum degree of 220 mTorr, and the plasma discharge is started.
And introducing reaction raw material steam, namely atomizing and volatilizing the reaction raw materials through a feed pump, into the reaction cavity at low pressure of 150 mTorr, wherein the flow of the introduced reaction raw materials is 120 mu L/min.
The components of the reaction raw materials are as follows:
the unsaturated fluorocarbon in the reaction raw materials is as follows:
in the step (2), the power of the plasma discharge is turned on to be 240W, and the plasma discharge mode is plasma pulse discharge.
In the step (3), the vacuum degree of the reaction cavity is kept at 160 mTorr, and after 4min, the atmosphere is introduced to one atmosphere.
It will be appreciated that the manner of plasma discharge may be adjusted as required.
Example 5
The basic process steps of the present example are the same as those of example 1, and the different process parameters are as follows:
in the step (1), the vacuum degree in the reaction cavity is pumped to 150 millitorr, nitrogen is introduced, wherein the substrate is a solid material, the solid material is an electrical component, and any interface of the substrate surface after the waterproof coating is prepared can be exposed to the environment of international industrial waterproof grade standard IPX6 for use.
In the step (1), the volume of the reaction chamber is 560L, the temperature of the reaction chamber is controlled at 50 ℃, and the flow rate of introducing nitrogen as a plasma source is 220 sccm.
In the step (2), the reaction material is introduced to a vacuum degree of 220 mTorr, and the plasma discharge is started.
In the step (2), the reaction raw material steam is introduced into the reaction cavity by introducing the reaction raw material into the reaction cavity through a feeding pump for atomization and volatilization, wherein the low pressure is 150 mTorr, and the flow rate of the introduced reaction raw material is 320 mu L/min.
The components of the reaction raw materials are as follows:
the unsaturated fluorocarbon in the reaction raw materials is as follows:
the polyfunctional unsaturated hydrocarbon derivatives as the crosslinking agent in the reaction raw materials are: ethylene glycol diacrylate, wherein the mass fraction ratio of the unsaturated fluorocarbon compound to the unsaturated hydrocarbon derivative is 55%: 45 percent.
In the step (2), the power of the plasma discharge is turned on to be 240W, the duration of the discharge is 3200 seconds, and the plasma discharge mode is microwave discharge.
In the step (3), the vacuum degree of the reaction cavity is kept at 160 mTorr, and after 4min, the atmosphere is introduced to one atmosphere.
Comparative example 6, prepared under the same conditions as in example 4, was another substrate, except that the unsaturated fluorocarbon in the reaction feed described in comparative example 6 was:
the hydrophobic property tests were performed for the above examples, respectively, and the test results are shown in the following table, the test methods are as follows:
the film thickness was measured using a film thickness measuring apparatus, U.S. Filmetrics F20-UV-film thickness measuring apparatus.
And (4) testing the water contact angle of the film layer according to the GB/T30447-2013 standard.
Further, the waterproof film layer obtained in example 4, the data related to the test are shown below,
| coating time | Thickness of the nanolayered coating | Water drop angle | Standing for 30min |
| 20min | 10nm | 115° | 115±1° |
| 40min | 20nm | 120° | 120±1° |
The waterproof film layer obtained in comparative example 6 was tested with the following data,
| coating time | Thickness of the nanolayered coating | Water drop angle | Standing for 10min |
| 20min | 10nm | 110° | <100° |
| 40min | 20nm | 112° | <100° |
As can be seen from comparing the two tables, the waterproof performance of the waterproof film layer in example 4 is stable, and it is noted that the carbon atom of the perfluoroalkyl group of the unsaturated fluorocarbon compound in example 4 is 6. That is, the present invention provides the waterproof film layer capable of providing excellent waterproof performance while reducing environmental pollution when the number of carbon atoms of the perfluoroalkyl group of the raw material is less than 8.
Further, the present invention provides further examples and comparative examples, as follows:
the invention provides example 7 and comparative example 8, as follows:
example 7
The basic process steps of the present example are the same as those of example 1, and the different process parameters are as follows:
in the step (1), the vacuum degree in the reaction chamber is pumped to 160 mTorr, and argon is introduced.
The substrate is a solid material which is an electrical appliance part, and any interface of the substrate surface after the waterproof coating is prepared can be exposed to the environment of the international industrial waterproof grade standard IPX5 for use.
The volume of the reaction cavity is 550L, the temperature of the reaction cavity is controlled at 45 ℃, and the flow of argon introduced as a plasma source is 200 sccm.
In the step (2), the reaction raw material is introduced to a vacuum degree of 200 mTorr, and plasma discharge is started.
And introducing reaction raw material steam, namely atomizing and volatilizing the reaction raw materials through a charging pump, into the reaction cavity at low pressure of 150 mTorr, wherein the flow of the introduced reaction raw materials is 150 mu L/min.
The components of the reaction raw materials are as follows:
the unsaturated fluorocarbon in the reaction raw materials is as follows:
in the step (2), the power of the plasma discharge is started to be 200W, and the plasma discharge mode is plasma discharge.
In the step (3), the vacuum degree of the reaction cavity is kept at 160 mTorr, and after 4min, the atmosphere is introduced to one atmosphere.
It will be appreciated that the manner of plasma discharge may be adjusted as required.
Comparative example 8 the waterproofing membrane layer was prepared on the same other substrate under the same conditions as in example 7, except that the unsaturated fluorocarbon compound in the reaction raw materials in comparative example 8 was:
for the above examples, the hydrophobic property tests were performed separately by the following methods:
the film thickness was measured using a film thickness measuring apparatus, U.S. Filmetrics F20-UV-film thickness measuring apparatus.
And (4) testing the water contact angle of the film layer according to the GB/T30447-2013 standard.
The waterproof film layer obtained in example 7, the data related to the test are shown below,
| coating time | Thickness of the nanolayered coating | Water drop angle | Standing for 30min |
| 15min | 10nm | 116° | 116±1° |
| 30min | 20nm | 118° | 118±1° |
The waterproof film layer obtained in comparative example 8, the relevant data of the test are shown below,
| coating time | Thickness of the nanolayered coating | Water drop angle | Standing for 10min |
| 15min | 10nm | 105° | <100° |
| 30min | 20nm | 110° | <100° |
As can be seen from comparing the two tables, the waterproof performance of the waterproof film layer in example 7 is stable, and it is noted that the carbon atom of the perfluoroalkyl group of the unsaturated fluorocarbon compound in example 7 is 6. That is, the present invention provides the waterproof film layer capable of providing excellent waterproof performance while reducing environmental pollution when the number of carbon atoms of the perfluoroalkyl group of the raw material is less than 8.
Further, the present invention provides example 9 and comparative example 10 as follows:
example 9
The basic process steps of the present example are the same as those of example 1, and the different process parameters are as follows:
in the step (1), the vacuum degree in the reaction chamber is pumped to 150 mTorr, and helium is introduced.
The substrate is a solid material which is an electrical appliance part, and any interface of the substrate surface after the waterproof coating is prepared can be exposed to the environment of the international industrial waterproof grade standard IPX4 for use.
The volume of the reaction cavity is 550L, the temperature of the reaction cavity is controlled at 40 ℃, and the flow rate of introducing helium as a plasma source is 200 sccm.
In the step (2), the reaction raw material is introduced to a vacuum degree of 200 mTorr, and plasma discharge is started.
And introducing reaction raw material steam, namely atomizing and volatilizing the reaction raw materials through a feed pump, into the reaction cavity from low pressure of 120 mTorr, wherein the flow of the introduced reaction raw materials is 200 mu L/min.
The components of the reaction raw materials are as follows:
the unsaturated fluorocarbon in the reaction raw materials is as follows:
in the step (2), the power of the plasma discharge is started to be 250W, and the plasma discharge mode is plasma pulse discharge.
In the step (3), the vacuum degree of the reaction cavity is kept at 150 mTorr, and after 4min, the atmosphere is introduced to one atmosphere.
It will be appreciated that the manner of plasma discharge may be adjusted as required.
Comparative example 10 the waterproofing membrane layer was prepared on the same other substrate under the same conditions as in example 9, except that the unsaturated fluorocarbon compound in the reaction raw materials in comparative example 10 was:
for the above examples, the hydrophobic property tests were performed separately by the following methods:
the film thickness was measured using a film thickness measuring apparatus, U.S. Filmetrics F20-UV-film thickness measuring apparatus.
And (4) testing the water contact angle of the film layer according to the GB/T30447-2013 standard.
The waterproof film layer obtained in example 9, the data related to the test are shown below,
| coating time | Thickness of the nanolayered coating | Water drop angle | Standing for 30min |
| 10min | 10nm | 116° | 116±1° |
| 20min | 20nm | 120° | 120±1° |
The waterproof film layer obtained in comparative example 10 was tested as follows, and the water drop angle was less than 100 ° after being left for 10 minutes.
| Coating time | Thickness of the nanolayered coating | Water drop angle | Standing for 10min |
| 10min | 10nm | 105° | <100° |
| 20min | 20nm | 108° | <100° |
As can be seen from comparing the two tables, the waterproof performance of the waterproof film layer in example 9 is stable, and it is noted that the carbon atom of the perfluoroalkyl group of the unsaturated fluorocarbon compound in example 9 is 5. That is, the present invention provides the waterproof film layer capable of providing excellent waterproof performance while reducing environmental pollution when the number of carbon atoms of the perfluoroalkyl group of the raw material is less than 8.
Further, the present invention provides example 11 and comparative example 12 as follows:
example 11
The basic process steps of the present example are the same as those of example 1, and the different process parameters are as follows:
in the step (1), the vacuum degree in the reaction chamber is pumped to 120 mTorr, and a mixture of argon and helium is introduced.
The substrate is a solid material which is an electrical appliance part, and any interface of the substrate surface after the waterproof coating is prepared can be exposed to the environment of the international industrial waterproof grade standard IPX5 for use.
The volume of the reaction cavity is 500L, the temperature of the reaction cavity is controlled at 35 ℃, and the flow rate of introducing a mixture of argon and helium as a plasma source is 200 sccm.
In the step (2), the reaction raw material is introduced to a vacuum degree of 200 mTorr, and plasma discharge is started.
And introducing reaction raw material steam, namely atomizing and volatilizing the reaction raw materials through a charging pump, into the reaction cavity at low pressure of 150 mTorr, wherein the flow of the introduced reaction raw materials is 180 mu L/min.
The components of the reaction raw materials are as follows:
the unsaturated fluorocarbon in the reaction raw materials is as follows:
in the step (2), the power of the plasma discharge is started to be 300W, and the plasma discharge mode is plasma pulse discharge.
In the step (3), the vacuum degree of the reaction cavity is kept at 160 mTorr, and after 4min, the atmosphere is introduced to one atmosphere.
It will be appreciated that the manner of plasma discharge may be adjusted as required.
Comparative example 12 the waterproofing membrane layer was prepared on the same other substrate under the same conditions as in example 11, except that the unsaturated fluorocarbon compound in the reaction raw materials in comparative example 11 was:
for the above examples, the hydrophobic property tests were performed separately by the following methods:
the film thickness was measured using a film thickness measuring apparatus, U.S. Filmetrics F20-UV-film thickness measuring apparatus.
And (4) testing the water contact angle of the film layer according to the GB/T30447-2013 standard.
The waterproof film layer obtained in example 11 has the following data related to the test, and the contact angle is 115-120 degrees.
| Coating time | Nano-coatingThickness of | Water drop angle | Standing for 30min |
| 12min | 10nm | 115° | 115±1° |
| 25min | 20nm | 120° | 120±1° |
The waterproof film layer obtained in comparative example 12 was tested as shown below, and the water drop angle was less than 100 ° after being left for 10 minutes.
| Coating time | Thickness of the nanolayered coating | Water drop angle | Standing for 10min |
| 12min | 10nm | 103° | <100° |
| 25min | 20nm | 105° | <100° |
As can be seen from comparing the two tables, the waterproof performance of the waterproof film layer in example 11 is stable, and it is noted that the carbon atom of the perfluoroalkyl group of the unsaturated fluorocarbon compound in example 11 is 5. That is, the present invention provides the waterproof film layer capable of providing excellent waterproof performance while reducing environmental pollution when the number of carbon atoms of the perfluoroalkyl group of the raw material is less than 8.
Further, the present invention provides example 13 and comparative example 14, as follows:
example 13
The basic process steps of the present example are the same as those of example 1, and the different process parameters are as follows:
in the step (1), the vacuum degree in the reaction chamber is pumped to 100 mTorr, and argon is introduced.
The substrate is a solid material which is an electrical appliance part, and any interface of the substrate surface after the waterproof coating is prepared can be exposed to the environment of the international industrial waterproof grade standard IPX5 for use.
The volume of the reaction cavity is 1000L, the temperature of the reaction cavity is controlled at 50 ℃, and the flow of argon introduced as a plasma source is 200 sccm.
In the step (2), the reaction raw material is introduced to a vacuum degree of 200 mTorr, and plasma discharge is started.
And introducing reaction raw material steam, namely atomizing and volatilizing the reaction raw materials through a feeding pump, into the reaction cavity from low pressure of 200 mTorr, wherein the flow of the introduced reaction raw materials is 100 mu L/min.
The components of the reaction raw materials are as follows:
the unsaturated fluorocarbon in the reaction raw materials is as follows:
in the step (2), the power of the plasma discharge is started to be 200W, and the plasma discharge mode is plasma pulse discharge.
In the step (3), the vacuum degree of the reaction cavity is kept at 160 mTorr, and after 4min, the atmosphere is introduced to one atmosphere.
It will be appreciated that the manner of plasma discharge may be adjusted as required.
Comparative example 14 the waterproofing membrane layer was prepared on the same other substrate under the same conditions as in example 13, except that the unsaturated fluorocarbon compound in the reaction raw materials in comparative example 14 was:
for the above examples, the hydrophobic property tests were performed separately by the following methods:
the film thickness was measured using a film thickness measuring apparatus, U.S. Filmetrics F20-UV-film thickness measuring apparatus.
And (4) testing the water contact angle of the film layer according to the GB/T30447-2013 standard.
The waterproof film layer obtained in example 13 has the following data related to the test, and the contact angle is 117 degrees and 121 degrees.
| Coating time | Thickness of the nanolayered coating | Water drop angle | Standing for 30min |
| 23min | 10nm | 117° | 117±1° |
| 45min | 20nm | 121° | 121±1° |
The waterproof film layer obtained in comparative example 14 was tested as follows, and the water drop angle was less than 100 ° after being left for 10 minutes.
| Coating time | Thickness of the nanolayered coating | Water drop angle | Standing for 10min |
| 23min | 10nm | 105° | <100° |
| 45min | 20nm | 107° | <100° |
As can be seen from comparing the two tables, the waterproof performance of the waterproof film layer in example 13 is stable, and it is noted that the carbon atom of the perfluoroalkyl group of the unsaturated fluorocarbon compound in example 13 is 6. That is, the present invention provides the waterproof film layer capable of providing excellent waterproof performance while reducing environmental pollution when the number of carbon atoms of the perfluoroalkyl group of the raw material is less than 8.
Further, the present invention provides example 15 and comparative example 16 as follows:
example 15
The basic process steps of the present example are the same as those of example 1, and the different process parameters are as follows:
in the step (1), the vacuum degree in the reaction chamber is pumped to 150 mTorr, and nitrogen is introduced.
The substrate is a solid material which is an electrical appliance part, and any interface of the substrate surface after the waterproof coating is prepared can be exposed to the environment of the international industrial waterproof grade standard IPX6 for use.
The volume of the reaction cavity is 560L, the temperature of the reaction cavity is controlled at 50 ℃, and the flow rate of introducing nitrogen as a plasma source is 220 sccm.
In the step (2), the reaction material is introduced to a vacuum degree of 220 mTorr, and the plasma discharge is started.
And introducing reaction raw material steam, namely atomizing and volatilizing the reaction raw materials through a feed pump, into the reaction cavity at low pressure of 150 mTorr, wherein the flow of the introduced reaction raw materials is 320 mu L/min.
The components of the reaction raw materials are as follows:
the unsaturated fluorocarbon in the reaction raw materials is as follows:
in the step (2), the power of the plasma discharge is turned on to be 240W, and the plasma discharge mode is plasma pulse discharge.
In the step (3), the vacuum degree of the reaction cavity is kept at 160 mTorr, and after 4min, the atmosphere is introduced to one atmosphere.
It will be appreciated that the manner of plasma discharge may be adjusted as required.
Comparative example 16 the waterproofing membrane layer was prepared on the same other substrate under the same conditions as in example 15 except that the unsaturated fluorocarbon compound in the reaction raw materials in comparative example 16 was:
for the above examples, the hydrophobic property tests were performed separately by the following methods:
the film thickness was measured using a film thickness measuring apparatus, U.S. Filmetrics F20-UV-film thickness measuring apparatus.
And (4) testing the water contact angle of the film layer according to the GB/T30447-2013 standard.
The waterproof film layer obtained in example 15 has the following data related to the test, and the contact angle is 115-122 degrees.
| Coating time | Thickness of the nanolayered coating | Water drop angle | Standing for 30min |
| 7min | 10nm | 115° | 115±1° |
| 14min | 20nm | 122° | 122±1° |
The waterproof film layer obtained in comparative example 16 was tested as follows, and the water drop angle was less than 100 ° after being left for 10 minutes.
| Coating time | Thickness of the nanolayered coating | Water drop angle | Standing for 10min |
| 7min | 10nm | 110° | <100° |
| 14min | 20nm | 112° | <100° |
As can be seen from comparing the two tables, the waterproof performance of the waterproof film layer in example 15 is stable, and it is noted that the carbon atom of the perfluoroalkyl group of the unsaturated fluorocarbon compound in example 15 is 6. That is, the present invention provides the waterproof film layer capable of providing excellent waterproof performance while reducing environmental pollution when the number of carbon atoms of the perfluoroalkyl group of the raw material is less than 8.
It will be appreciated by persons skilled in the art that the embodiments of the invention shown in the foregoing description are by way of example only and are not limiting of the invention. The objects of the invention have been fully and effectively accomplished. The functional and structural principles of the present invention have been shown and described in the examples, and any variations or modifications of the embodiments of the present invention may be made without departing from the principles.
Claims (15)
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 is1、R2And R3Independently selected from hydrogen, alkyl, halogen, haloalkyl or aryl, wherein R is1、R2And R3Is halogen, wherein R is4Is a group X-R5，R5Is alkyl or is a haloalkyl group and X is a bond; or X is a group-C (O) O (CH)2)nY-, wherein n is an integer of 0 to 10, and Y is a bond or a sulfonamide group; or X is a group-O-C (O) - (CH)2)iZ-, wherein i is an integer of 1 to 10, and Z is a bond or a sulfonamide group; or X is a group- (CH)2)xU-, wherein x is an integer of 1 to 10, and U is a bond or a sulfonamide group; or X is a group- (O)pR6(O)q(CH2)t-, wherein R6Is aryl optionally substituted with halogen, p is 0 or 1, q is 0 or 1 and t is 0 or an integer from 1 to 10, with the proviso that when q is 1, t is not 0.
2. The waterproofing membrane layer according to claim 1 wherein the compound of formula (I) is embodied as a compound of formula (II),
wherein R is3Is halogen, R4Is a group-R5Or is a group-C (O) O (CH)2)nR5Or is a group-O-C (O) - (CH)2)iR5，R5Is a haloalkyl group.
3. The waterproofing membrane layer according to claim 2, wherein R5Is a perhaloalkyl group.
4. The waterproof film layer according to claim 2, wherein n is an integer of 1 to 8.
5. The waterproofing membrane layer according to any one of claims 1 to 4, wherein R5Is of the general formula CmF2m+1A group of (1).
6. The waterproof film layer according to claim 5, wherein m is an integer of 1 to 8.
7. A product having a water-repellent film layer, characterized in that the product is provided with a water-repellent film layer formed on the surface of the product by a plasma chemical vapor deposition method using one or more compounds of the general formula (I),
wherein R is1、R2And R3Independently selected from hydrogen, alkyl, halogen, haloalkyl or aryl, wherein R is1、R2And R3Is halogen, wherein R is4Is a group X-R5，R5Is an alkyl or haloalkyl group and X is oneA key; or X is a group-C (O) O (CH)2)nY-, wherein n is an integer of 0 to 10, and Y is a bond or a sulfonamide group; or X is a group-O-C (O) - (CH)2)iZ-, wherein i is an integer of 1 to 10, and Z is a bond or a sulfonamide group; or X is a group- (CH)2)xU-, wherein x is an integer of 1 to 10, and U is a bond or a sulfonamide group; or X is a group- (O)pR6(O)q(CH2)t-, wherein R6Is aryl optionally substituted with halogen, p is 0 or 1, q is 0 or 1 and t is 0 or an integer from 1 to 10, with the proviso that when q is 1, t is not 0.
8. The product of claim 7, 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.
9. The product of claim 7, wherein the waterproofing membrane layer disposed on the product is prepared from a compound of formula (II),
wherein R is3Is halogen, R4Is a group-R5Or is a group-C (O) O (CH)2)nR5Or is a group-O-C (O) - (CH)2)iR5，R5Is a haloalkyl group.
10. The product of claim 7, wherein R5Is a perhaloalkyl group.
11. The product of claim 10, wherein R5Is of the general formula CmF2m+1A group of (1).
12. 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 is1、R2And R3Independently selected from hydrogen, alkyl, halogen, haloalkyl or aryl, wherein R is1、R2And R3Is halogen, wherein R is4Is a group X-R5，R5Is alkyl or is a haloalkyl group and X is a bond; or X is a group-C (O) O (CH)2)nY-, wherein n is an integer of 0 to 10, and Y is a bond or a sulfonamide group; or X is a group-O-C (O) - (CH)2)iZ-, wherein i is an integer of 1 to 10, and Z is a bond or a sulfonamide group; or X is a group- (CH)2)xU-, wherein x is an integer of 1 to 10, and U is a bond or a sulfonamide group; or X is a group- (O)pR6(O)q(CH2)t-, wherein R6Is aryl optionally substituted with halogen, p is 0 or 1, q is 0 or 1 and t is 0 or an integer from 1 to 10, with the proviso that when q is 1, t is not 0.
13. The method of claim 12, comprising the steps of: before the reaction gas raw materials are introduced, a plasma source gas is introduced for activating the chemical deposition reaction of the reaction gas raw materials.
14. The method of claim 13, wherein the plasma source gas is selected from the group consisting of: one or two of inert gas and fluorocarbon gas.
15. The method according to claim 13, wherein in the above method, the reaction raw material further comprises a crosslinking agent, wherein the crosslinking agent is a multifunctional compound.
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