阅读说明：本技术 防水纳米膜及其制备方法、应用和产品 (Waterproof nano film and preparation method, application and product thereof ) 是由 宗坚 于 2019-08-02 设计创作，主要内容包括：本发明提供一防水纳米膜及其制备方法、应用和产品,其中所述防水纳米膜以氟碳气体作为等离子体源,通过等离子体增强化学气相沉积方法在一基体表面形成,由此提高基体表面的防水性能。(The invention provides a waterproof nano film, a preparation method, application and a product thereof, wherein the waterproof nano film takes fluorocarbon gas as a plasma source and is formed on the surface of a substrate by a plasma enhanced chemical vapor deposition method, so that the waterproof performance of the surface of the substrate is improved.)

1. The waterproof nanometer film is characterized in that fluorocarbon gas is used as a plasma source and is formed on the surface of a substrate by a plasma enhanced chemical vapor deposition method.

2. The waterproof nanomembrane of claim 1, wherein the fluorocarbon gas has the structural formula: c_xF_2x+2Or C_xF_2xWherein x is 1,2, 3.

3. The waterproof nanomembrane of claim 1, wherein the fluorocarbon gas is selected from one of carbon tetrafluoride, tetrafluoroethylene, hexafluoroethane.

4. The waterproof nanomembrane of claim 1, wherein the waterproof nanomembrane has a static contact angle selected from the group consisting of: 110-115 degrees, 115-120 degrees, 120-125 degrees, 125-130 degrees, 130-135 degrees, 135-140 degrees, 140-145 degrees and 145-150 degrees.

5. The waterproof nanomembrane of any one of claims 1 to 4, wherein the waterproof nanomembrane is vapor deposited using one, two, or three of monomer 1, monomer 2, and monomer 3 as a reaction raw material.

6. The waterproof nanomembrane of claim 5, wherein the monomer 1 has the structural formula (I): Y-C_mH_2m-C_nF_2n+1M is an integer of 0 to 4, n is an integer of 1 to 12, and Y is an organic functional group.

7. The waterproof nanomembrane of claim 5, wherein m is an integer from 0 to 2.

8. The waterproof nanomembrane of claim 5, wherein n is an integer from 1 to 7.

9. The waterproof nanomembrane of claim 5, wherein Y is selected from the group consisting of: vinyl, halogen-substituted vinyl, alkyl-substituted vinyl; an acrylate group; c ═ C-O-C (O); or a methacrylate group; hydroxy, halogen; (C)_pH_2p+1O_q)3 Si-wherein p is an integer of 0 to 4 and q is an integer of 0 to 2.

10. The waterproof nanomembrane of claim 9, wherein p is 1 or 2 and q is 1.

11. The waterproof nanomembrane of claim 5, wherein the monomer 2 has structural formula (II):

wherein R is₁、R₂、R₃、R₄、R₅、R₆Each selected from the group consisting of hydrogen, alkyl, aryl, haloaryl, halogen, haloalkyl, alkoxy, vinyl, and k is an integer from 0 to 4.

12. The waterproof nanomembrane of claim 11, wherein k is 0-2.

13. The waterproof nanomembrane of claim 5, wherein the monomer 3 has structural formula (III):

wherein R is₇、R₈、R₉、R₁₀、R₁₁、R₁₂Each selected from hydrogen, alkyl, aryl, halogen, haloalkyl, haloaryl, j, k are integers from 0 to 10 and cannot be 0 at the same time, R₁₃Is a bond, -CO-, -COO-, an aromatic subunit, an alicyclic alkyl subunit, a hydroxyl-substituted aliphatic alkyl subunit.

14. The waterproof nanomembrane of claim 5, wherein the monomer 3 is a multifunctional compound containing ester groups, ethers, epoxy groups, and/or cyano groups.

15. The waterproof nanomembrane of claim 5, wherein the monomer 3 is selected from the group consisting of: one or more of glycidyl methacrylate, allyl glycidyl ether, 1, 2-epoxy-4-vinylcyclohexane, 3- (2, 3-glycidoxy) propyl vinyl dimethoxy silane and enbuester.

16. The waterproof nanomembrane of any of claims 1 to 4 or 6 to 15, wherein the matrix is selected from the group consisting of: one of electronic products, silk fabrics, woven bags, metal products, glass products and ceramic products.

17. The waterproof nanomembrane of any of claims 1 to 4 or 6 to 15, wherein the waterproof nanomembrane has a thickness ranging from: 10 to 2000 nm.

18. The preparation method of the waterproof nanometer film is characterized in that fluorocarbon gas is used as a plasma source gas, and plasma enhanced chemical vapor deposition is carried out on the surface of a substrate through a PECVD device.

19. The method of preparing a waterproof nanomembrane of claim 18, wherein the fluorocarbon gas has the structural formula: c_xF_2x+2Or C_xF_2xWherein x is 1,2, 3.

20. The method of preparing a waterproof nanomembrane of claim 19, wherein the fluorocarbon gas is selected from one of carbon tetrafluoride, tetrafluoroethylene, and hexafluoroethane.

21. The method of preparing a waterproof nanomembrane of claim 18, wherein the waterproof nanomembrane has a static contact angle selected from the group consisting of: 110-115 degrees, 115-120 degrees, 120-125 degrees, 125-130 degrees, 130-135 degrees, 135-140 degrees, 140-145 degrees and 145-150 degrees.

22. The method for preparing a waterproof nanomembrane according to any one of claims 18 to 21, wherein the waterproof nanomembrane is vapor-deposited using one, two, or three of monomer 1, monomer 2, and monomer 3 as a reaction raw material.

23. The method of preparing a waterproof nanomembrane of claim 22, wherein the monomer 1 has the structural formula (I): Y-C_mH_2m-C_nF_2n+1M is an integer of 0 to 4, n is an integer of 1 to 12, and Y is an organic functional group.

24. The method of preparing a waterproof nanomembrane of claim 22, wherein m is an integer of 0 to 2.

25. The method of preparing a waterproof nanomembrane of claim 22, wherein n is an integer of 1 to 7.

26. The method of preparing a waterproof nanomembrane of claim 22, wherein Y is selected from the group consisting of: vinyl, halogen-substituted vinyl, alkyl-substituted vinyl; an acrylate group; c ═ C-O-C (O); or methacrylic acid estersA group; hydroxy, halogen; (C)_pH_2p+1O_q)3 Si-wherein p is an integer of 0 to 4 and q is an integer of 0 to 2.

27. The method of preparing a waterproof nanomembrane of claim 26, wherein p is 1 or 2 and q is 1.

28. The method of preparing a waterproof nanomembrane of claim 22, wherein the monomer 2 has structural formula (II):

wherein R is₁、R₂、R₃、R₄、R₅、R₆Each selected from the group consisting of hydrogen, alkyl, aryl, haloaryl, halogen, haloalkyl, alkoxy, vinyl, and k is an integer from 0 to 4.

29. The method of preparing a waterproof nanomembrane of claim 28, wherein k is 0 to 2.

30. The method of preparing a waterproof nanomembrane of claim 22, wherein the monomer 3 has the structural formula (III):

wherein R is₇、R₈、R₉、R₁₀、R₁₁、R₁₂Each selected from hydrogen, alkyl, aryl, halogen, haloalkyl, haloaryl, j, k are integers from 0 to 10 and cannot be 0 at the same time, R₁₃Is a bond, -CO-, -COO-, an aromatic subunit, an alicyclic alkyl subunit, a hydroxyl-substituted aliphatic alkyl subunit.

31. The method of preparing a waterproof nanomembrane according to claim 22, wherein the monomer 3 is a multifunctional compound having an ester group, an ether group, an epoxy group, and/or a cyano group.

32. The method of preparing a waterproof nanomembrane of claim 22, wherein the monomer 3 is selected from the group consisting of: one or more of glycidyl methacrylate, allyl glycidyl ether, 1, 2-epoxy-4-vinylcyclohexane, 3- (2, 3-glycidoxy) propyl vinyl dimethoxy silane and enbuester.

33. The method of preparing a waterproof nanomembrane of any one of claims 18 to 21 or 23 to 32, wherein the substrate is selected from the group consisting of: one of electronic products, silk fabrics, woven bags, metal products, glass products and ceramic products.

34. The method of preparing a waterproof nanomembrane according to any one of claims 18 to 21 or 23 to 32, wherein the waterproof nanomembrane has a thickness ranging from: 10 to 2000 nm.

35. The method for preparing a waterproof nanomembrane according to any one of claims 18 to 21 or 23 to 32, wherein the PECVD apparatus has a discharge power ranging from: 30-200 w.

36. The method for preparing a waterproof nanomembrane according to any one of claims 18 to 21 or 23 to 32, wherein a pressure of a reaction chamber of the PECVD apparatus is in a range of: 10 mTorr to 500 mTorr.

37. The method for preparing a waterproof nanomembrane according to any one of claims 18 to 21 or 23 to 32, wherein a reaction chamber of the PECVD apparatus has a temperature ranging from: 30-60 ℃.

38. The method for preparing a waterproof nanomembrane according to any one of claims 18 to 21 or 23 to 32, which comprises the steps of: the substrate is operated such that the substrate moves within a chamber of a PECVD apparatus.

39. A method of waterproofing a substrate surface, characterized by exposing the substrate to a waterComprising the structural formula: c_xF_2x+2Or C_xF_2xAdding reaction raw materials into the plasma source atmosphere to carry out plasma enhanced chemical vapor deposition so as to form the waterproof nano film on the surface of the substrate, wherein x is 1,2 or 3.

40. A method of waterproofing a substrate surface according to claim 39, wherein the reaction raw material is selected from the group consisting of: one, two or three of monomer 1, monomer 2 and monomer 3, wherein monomer 1 has the structural formula (I): Y-C_mH_2m-C_nF_2n+1M is an integer of 0 to 4, n is an integer of 1 to 12, and Y is an organic functional group; the monomer 2 has the structural formula (II):

wherein R is₁、R₂、R₃、R₄、R₅、R₆Each selected from the group consisting of hydrogen, alkyl, aryl, haloaryl, halogen, haloalkyl, alkoxy, vinyl, k is an integer from 0 to 4; the monomer 3 has the structural formula (III):

wherein R is₇、R₈、R₉、R₁₀、R₁₁、R₁₂Each selected from hydrogen, alkyl, aryl, halogen, haloalkyl, haloaryl, j, k are integers from 0 to 10 and cannot be 0 at the same time, R₁₃Is a bond, -CO-, -COO-, an aromatic subunit, an alicyclic alkyl subunit, a hydroxyl-substituted aliphatic alkyl subunit.

41. The method of waterproofing a substrate surface according to claim 39, wherein the substrate is selected from the group consisting of: one of electronic products, silk fabrics, woven bags, metal products, glass products and ceramic products.

42. A product having water-repellent nanomembranes produced by exposing said product to a composition comprising the structural formula: c_xF_2x+2Or C_xF_2xIs prepared by performing plasma enhanced chemical vapor deposition on reaction raw materials so that a waterproof nano film is formed on at least part of the surface of the product, wherein x is 1,2 or 3.

43. The product with water repellent nanomembrane of claim 42, wherein the reaction raw material is selected from the group consisting of: one, two or three of monomer 1, monomer 2 and monomer 3, wherein monomer 1 has the structural formula (I): Y-C_mH_2m-C_nF_2n+1M is an integer of 0 to 4, n is an integer of 1 to 12, and Y is an organic functional group; the monomer 2 has the structural formula (II):

wherein R is₁、R₂、R₃、R₄、R₅、R₆Each selected from the group consisting of hydrogen, alkyl, aryl, haloaryl, halogen, haloalkyl, alkoxy, vinyl, k is an integer from 0 to 4; the monomer 3 has the structural formula (III):

wherein R is₇、R₈、R₉、R₁₀、R₁₁、R₁₂Each selected from hydrogen, alkyl, aryl, halogen, haloalkyl, haloaryl, j, k are integers from 0 to 10 and cannot be 0 at the same time, R₁₃Is a bond, -CO-, -COO-, an aromatic subunit, an alicyclic alkyl subunit, a hydroxyl-substituted aliphatic alkyl subunit.

44. The product with water repellent nanomembrane of claim 42, wherein the product is selected from the group consisting of: one of electronic products, silk fabrics, woven bags, metal products, glass products and ceramic products.

Technical Field

The present invention relates to a surface-modified thin film, and more particularly, to a water-repellent nano-film formed using a plasma-enhanced chemical vapor deposition method, and a method for preparing the same, applications thereof, and products thereof.

Background

The surface modification of the substrate by depositing a thin film on the surface of the substrate is a common technique, for example, the dielectric property, the water resistance or the hydrophobic property are improved by depositing the thin film. Deposition of thin films can be accomplished by a number of techniques, well known techniques including chemical deposition, physical deposition and a mixture of both. For chemical deposition, techniques such as plating, Chemical Solution Deposition (CSD), and Chemical Vapor Deposition (CVD) are relatively common. For physical deposition, well-known techniques such as thermal evaporation, sputtering, pulsed laser deposition, and cathodic arc deposition.

Fluorine atoms in the fluorocarbon material have low polarizability and strong electronegativity, so that the fluorocarbon polymer has many unique properties such as high hydrophobicity and oleophobicity, chemical reagent corrosion resistance, excellent weather resistance and the like, and is widely applied to the fields of building coatings, textile industry, military industry and the like for surface modification.

According to research, the hydrophobicity of the fluorocarbon material is closely related to the length of the perfluorocarbon chain of the fluorocarbon material, and the crystallinity is improved along with the increase of the number of carbon atoms of the perfluorocarbon chain. The hydrophobic performance of the fabric is improved, and the fabric is widely applicable to organic matters with perfluoroalkyl groups with carbon atoms of more than 8. In contrast, when the number of carbon atoms in the alkyl group is 6 or less, the hydrophobicity is significantly reduced, and it is difficult to meet the demand of practical use. However, the use of long-carbon-chain perfluoroalkyl groups in large quantities tends to produce environmentally harmful and recalcitrant organics like PFOA, PFOS, etc. Since 2003, the USEPA proposed that PFOA and its primary salt exposure could lead to adverse effects on the development of health and other aspects, and that PFOA was also banned under the influence of europe in the united states under general safety standards (food contact materials and substances resolution) as mandated by european union 2004/1935/EC; 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.

CN 102471405 a "N-substituted (meth) acrylamide compound containing fluoroalkyl group, its polymer and its use", in which a protective layer is formed by coating a liquid of N-substituted (meth) acrylamide compound containing fluoroalkyl group on the surface of a sample to be treated, the purposes of rust prevention, hydrophobicity, etc. are achieved, and excellent hydrophobicity can be maintained even at a carbon number of 6 or less without being limited by the use of PFOA and PFOA analogues. The product obtained in the invention is generally prepared into a solution with a certain concentration by using an organic solvent, preferably a fluorine-based solvent before use, and then is coated on the surface of an object. This liquid phase coating method has many disadvantages: the liquid phase method can generate waste water, waste gas and waste liquid, the used solvent can generate certain damage to the electronic device substrate, in addition, the thickness of the electronic device substrate is mostly dozens of micrometers, the electronic device substrate is difficult to control at a nanometer level, and certain influence can be brought to the functions of some electronic devices needing heat dissipation and signal transmission.

Plasma Chemical Vapor Deposition (PCVD) is a technique in which plasma activates a reaction gas to perform a chemical reaction on a substrate surface or a near-surface space to generate a solid film, and belongs to one of chemical deposition processes.

When the PCVD is adopted for the nano coating process, firstly, plasma source gas is needed to form plasma, and then reaction raw material gas reacts in the plasma atmosphere to be gradually deposited on the surface of the substrate. The plasma source gas raw material and the reaction raw material are two main raw materials, and the basic performance of the formed film is influenced. For example, at the beginning of the reaction, some inert gas such as He, Ar, etc. is often added as a plasma source to increase the plasma concentration inside the reaction chamber and maintain the necessary equilibrium concentration of plasma during the coating process [ Hubert, j.; vandencasteele, n.; mertens, J.et.chemical and Physical Effects of the Carrier Gas on the atmospheric pressure PECVD of Fluorinated compressors. Plasma Processes and Polymers 2015,12(10), 1174. sup. 1185 ]. Chinese patent CN107058982 provides a method for preparing a liquid-proof coating with a multilayer structure, wherein inert gas or nitrogen is introduced during the processing stage of the chemical vapor deposition process and the coating deposition process, and the inert gas is helium or argon. US patent 6663713 discloses a method and apparatus for forming a thin polymer layer on a semiconductor substrate, the deposition (and etching) on a substrate of any polymer or polymerisable dielectric material used in combination, including for example, xylylene, tetrafluoroethylene, polytetrafluoroethylene, naphthalene or polynaphthalene, a continuous supply of reactive polymerisable material being provided into the chamber through a gas inlet. The reactive polymerizable material is preferably supplied into the chamber using an inert carrier gas such as helium or argon. The inert gas and the RF bias can be used to form a plasma within the processing chamber. However, the inventors have found that when an inert gas is used as a plasma source, when the number of carbon atoms of the perfluorocarbon chain of the reaction raw material gas used is less than 6, particularly less than 4, the nano-coating obtained by plasma chemical vapor deposition generally has poor hydrophobicity, and even has a contact angle of less than 100 °.

Disclosure of Invention

An object of the present invention is to provide a waterproof nanomembrane, and a method for preparing the same, an application thereof, and a product thereof, which uses fluorocarbon gas as a plasma source, so that the plasma source itself has a high fluorine content, thereby increasing the fluorine content in the formed waterproof nanomembrane.

One purpose of the invention is to provide a waterproof nano-film, a preparation method, application and a product thereof, wherein fluorocarbon gas has the following structure: c_xF_2x+2Or C_xF_2xWherein x is 1,2 and 3, thereby obtaining the low-carbon high-fluorine plasma source.

An object of the present invention is to provide a waterproof nanomembrane, and a method for preparing the same, applications thereof, and products thereof, which improve the disadvantage of poor hydrophobicity of a nano coating deposited when the number of carbon atoms of a perfluorocarbon chain is less than 6.

The invention aims to provide a waterproof nano film, a preparation method, application and a product thereof, wherein the waterproof nano film with a static water contact angle of more than 110 degrees can be obtained by using reaction raw materials with the number of carbon atoms of a perfluorocarbon chain of 6 and less than 6.

The invention aims to provide a waterproof nano-film, a preparation method, application and a product thereof, wherein plasma formed by a fluorocarbon plasma source has stronger etching capability on the surface of a substrate, so that a rough structure is formed on the surface of the substrate, and the hydrophobicity can be improved and the bonding property of the nano-film and the substrate can be improved.

An object of the present invention is to provide a waterproof nanomembrane, and a method for preparing the same, applications thereof, and products thereof, which reduce environmental pollution from the viewpoint of raw materials and enable a nanomembrane layer formed by vapor deposition of environmentally friendly raw materials to have good hydrophobicity.

An object of the present invention is to provide a waterproof nanomembrane capable of being deposited on the surface of a substrate such as electronic products, silks, woven bags, metal products, glass products, ceramic products, etc., thereby imparting waterproof or liquid-proof properties to the surface of the substrate product, and a method for preparing the same, use thereof, and products thereof.

In order to achieve at least one of the above objectives, the present invention provides a waterproof nanomembrane, which is formed on a substrate surface by a plasma enhanced chemical vapor deposition method using fluorocarbon gas as a plasma source.

The waterproof nanomembrane of some embodiments, wherein the fluorocarbon gas has the structural formula: c_xF_2x+2Or C_xF_2xWherein x is 1,2, 3.

The water repellent nanomembrane according to some embodiments, wherein the fluorocarbon gas is selected from one of carbon tetrafluoride, tetrafluoroethylene, hexafluoroethane.

The waterproof nanomembrane of some embodiments, wherein the waterproof nanomembrane has a static contact angle selected from the group consisting of: 110-115 degrees, 115-120 degrees, 120-125 degrees, 125-130 degrees, 130-135 degrees, 135-140 degrees, 140-145 degrees and 145-150 degrees.

The waterproof nanomembrane according to some embodiments, wherein the waterproof nanomembrane is vapor deposited using one, two, or three of monomer 1, monomer 2, and monomer 3 as a reaction raw material.

The waterproof nanomembrane of some embodiments, wherein the monomer 1 has the structural formula (I): Y-C_mH_2m-C_nF_2n+1M is an integer of 0 to 4, n is an integer of 1 to 12, and Y is an organic functional group.

The waterproof nanomembrane according to some embodiments, wherein m is an integer from 0 to 2.

The waterproof nanomembrane according to some embodiments, wherein n is an integer from 1 to 7.

The waterproof nanomembrane of some embodiments, wherein Y is selected from the group consisting of: vinyl, halogen-substituted vinyl, alkyl-substituted vinyl; an acrylate group; c ═ C-O-C (O); or a methacrylate group; hydroxy, halogen; (C)_pH_2p+1O_q)3 Si-wherein p is an integer of 0 to 4 and q is an integer of 0 to 2.

The waterproof nanomembrane according to some embodiments, wherein p is 1 or 2 and q is 1.

The waterproof nanomembrane of some embodiments, wherein the monomer 2 has structural formula (II):

wherein R is₁、R₂、R₃、R₄、R₅、R₆Each selected from the group consisting of hydrogen, alkyl, aryl, haloaryl, halogen, haloalkyl, alkoxy, vinyl, and k is an integer from 0 to 4.

The waterproof nanomembrane according to some embodiments, wherein k is 0 to 2.

The waterproof nanomembrane of some embodiments, wherein the monomer 3 has the structural formula (III):

wherein R is₇、R₈、R₉、R₁₀、R₁₁、R₁₂Each selected from hydrogen, alkyl, aryl, halogen, haloalkyl, haloaryl, j, k are integers from 0 to 10 and cannot be 0 at the same time, R₁₃Is a bond, -CO-, -COO-, an aromatic subunit, an alicyclic alkyl subunit, a hydroxyl-substituted aliphatic alkyl subunit.

The waterproof nanomembrane according to some embodiments, wherein the monomer 3 is a multifunctional compound containing an ester group, an ether group, an epoxy group, and/or a cyano group.

The waterproof nanomembrane according to some embodiments, wherein the monomer 3 is selected from the group consisting of: one or more of glycidyl methacrylate, allyl glycidyl ether, 1, 2-epoxy-4-vinylcyclohexane, 3- (2, 3-glycidoxy) propyl vinyl dimethoxy silane and enbuester.

The waterproof nanomembrane according to some embodiments, wherein the matrix is selected from the group consisting of: one of electronic products, silk fabrics, woven bags, metal products, glass products and ceramic products.

The waterproof nanomembrane according to some embodiments, wherein the waterproof nanomembrane has a thickness ranging from: 10 to 2000 nm.

The invention also provides a preparation method of the waterproof nano film, which is characterized in that fluorocarbon gas is used as a plasma source gas, and plasma enhanced chemical vapor deposition is carried out on the surface of a substrate through a PECVD device.

The method for preparing a waterproof nanomembrane according to some embodiments, wherein the discharge power range of the PECVD apparatus is: 30-200 w.

The method for preparing a waterproof nanomembrane according to some embodiments, wherein a pressure range of a reaction chamber of the PECVD apparatus is: 10 mTorr to 500 mTorr.

The method for preparing a waterproof nanomembrane according to some embodiments, wherein a temperature range of a reaction chamber of the PECVD apparatus is: 30-60 ℃.

The method for preparing a waterproof nanomembrane according to some embodiments, comprising the steps of: the substrate is cleaned.

The method for preparing a waterproof nanomembrane according to some embodiments, comprising the steps of: the substrate is operated such that the substrate moves within a chamber of a PECVD apparatus.

In another aspect of the invention, a method of waterproofing a substrate surface is provided by exposing the substrate to a composition comprising the structural formula: c_xF_2x+2Or C_xF_2xIn the plasma source atmosphere, adding a reaction raw material to perform plasmaAnd (3) carrying out daughter-enhanced chemical vapor deposition to form the waterproof nano-film on the surface of the substrate, wherein x is 1,2 or 3.

The method of waterproofing a substrate surface according to some embodiments, wherein the reaction raw material is selected from the group consisting of: one, two or three of the monomers 1,2 and 3.

The method of waterproofing a substrate surface according to some embodiments, wherein the substrate is selected from the group consisting of: one of electronic products, silk fabrics, woven bags, metal products, glass products and ceramic products.

Another aspect of the present invention provides a product having a water-repellent nanomembrane by exposing the product to a composition comprising the structural formula: c_xF_2x+2Or C_xF_2xIs prepared by performing plasma enhanced chemical vapor deposition on reaction raw materials so that a waterproof nano film is formed on at least part of the surface of the product, wherein x is 1,2 or 3.

The product having a water repellent nanomembrane according to some embodiments, wherein the reaction raw material is selected from the group consisting of: one, two or three of the monomers 1,2 and 3.

The product having a water repellent nanomembrane according to some embodiments, wherein the product is selected from the group consisting of: one of electronic products, silk fabrics, woven bags, metal products, glass products and ceramic products.

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.

The invention provides a waterproof nano film and a preparation method and application thereof, wherein the waterproof nano film or nano coating contains carbon, hydrogen and fluorine. Preferably, the water-repellent nanomembrane contains oxygen, carbon, hydrogen, and fluorine. The waterproof nano film has good hydrophobicity or lyophobicity. That is, when the waterproof nanomembrane is attached to the surface of a substrate, the surface of the substrate can have good waterproofness, and damage of water or other liquid can be avoided.

In some embodiments, the substrate may be an electronic product, a silk fabric, a woven bag, a metal surface, a glass surface, a ceramic surface, or the like. That is, when the waterproof nanomembrane is attached to the surface of an electronic product, a silk fabric, a woven bag, a metal product, a glass product or a ceramic product, the waterproof nanomembrane can make the products have better waterproofness and avoid the damage of water or other liquids.

Further, when water adheres to the water repellent nanomembrane, the static contact angle of water is greater than 110 °, for example, greater than 120 °, for example, greater than 140 °, for example, in the range of: 110-115 degrees, 115-120 degrees, 120-125 degrees, 125-130 degrees, 130-135 degrees, 135-140 degrees, 140-145 degrees and 145-150 degrees. Thereby making the low dielectric constant film have good corrosion resistance. For example, when the low-k film is deposited on the substrate surface for a long time after salt spray test, the substrate surface is not corroded or has a small amount of corrosion spots, as shown in the following embodiments.

The waterproof nano film is a nano film with a smaller thickness, and the thickness range is exemplified but not limited to 10-2000 nm.

According to an embodiment of the present invention, the water-repellent nanomembrane is formed on the surface of the base body through a Plasma Enhanced Chemical Vapor Deposition (PECVD) process. That is, in the preparation process, the surface of the substrate is exposed to a chamber of a plasma enhanced chemical vapor deposition reaction device, plasma is formed in the chamber, and the waterproof nano-film is formed on the surface of the substrate through a reaction raw material deposition reaction.

Plasma Enhanced Chemical Vapor Deposition (PECVD) processes have many advantages over other existing deposition processes: (1) the dry film forming does not need to use organic solvent; (2) the plasma acts on the surface of the substrate in an etching way, so that the deposited film has good adhesion with the substrate; (3) the coating can be uniformly deposited on the surface of the irregular matrix, and the gas phase permeability is extremely strong; (4) the coating has good designability, and compared with the micron-scale control precision of a liquid phase method, the chemical vapor phase method can control the thickness of the coating at a nanoscale scale; (5) the coating structure is easy to design, the chemical vapor method uses plasma for activation, a specific initiator is not required to be designed for initiating the composite coatings of different materials, and various raw materials can be compounded together by regulating and controlling input energy; (6) the compactness is good, the chemical vapor deposition method usually activates a plurality of active sites in the plasma initiation process, and is similar to the situation that a plurality of functional groups are arranged on one molecule in the solution reaction, and a cross-linking structure is formed among molecular chains through the plurality of functional groups; (7) as a coating treatment technical means, the coating treatment method has excellent universality, and the selection range of coating objects and raw materials used for coating is wide.

The Plasma Enhanced Chemical Vapor Deposition (PECVD) process generates plasma through glow discharge, and the discharge method comprises microwave discharge, radio frequency discharge, ultraviolet, electric spark discharge and the like.

Further, according to some embodiments of the present invention, the water-repellent nano-film is formed by using fluorocarbon gas as a plasma source gas. That is, plasma is generated by the fluorocarbon gas to provide plasma atmosphere reaction conditions for the reaction raw material.

It is worth mentioning that in the existing PECVD process, most of the inert gases are used as the plasma source gas, such as helium or argon, to supply the reactive polymerizable material into the chamber, as described above. The inert gas and the RF bias can be used to form a plasma within the processing chamber. Experiments show that when inert gas is used as a plasma source, when the number of carbon atoms of a perfluorocarbon chain of a reaction raw material gas used is less than 6, particularly less than 4, the nano coating obtained by plasma chemical vapor deposition has poor hydrophobicity, and even the contact angle is less than 100 degrees. According to the embodiment of the present invention, the water-repellent nanomembrane uses fluorocarbon gas as a plasma source gas, and the reaction raw material gas contains perfluorocarbon chains, when the number of carbon atoms is low, and still has good hydrophobicity, such as a contact angle of more than 120 °.

Further, the plasma source gas forming the water repellent nanomembrane has the structural formula: c_xF_2x+2Or C_xF_2xWherein 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 other words, one of the raw materials of the waterproof nanomembrane is made to have a low carbon number, thereby reducing the formation of organic substances that are harmful to the environment and difficult to degrade. Preferably, the plasma source gas is selected from one of carbon tetrafluoride, tetrafluoroethylene, and hexafluoroethane.

It is also worth mentioning that the use of fluorocarbon gases as the plasma source has many advantages: (1) the plasma source has high fluorine content, correspondingly increases the fluorine content in the nano coating, and the increase of the fluorine content mainly improves the hydrophobic property; (2) even if the reaction raw materials with the number of carbon atoms of the perfluorocarbon chain of 6 and below are used, the nano coating with the water contact angle of more than 120 degrees can be obtained; (3) the etching capability of plasmas formed by the fluorocarbon plasma source to the surface of the substrate is stronger, a rough structure is formed on the surface of the substrate, the hydrophobicity can be improved, and the bonding performance of the coating and the substrate can also be improved.

Further, according to the embodiment of the present invention, in the process of forming the waterproof nanomembrane, the reactive raw material may be selected from compounds having structural monomers 1 and 2; to increase the degree of crosslinking of the nanocoating, monomer 3 may also be added. The monomer 1, the monomer 2 and the monomer 3 respectively have structures of formulas (I), (II) and (III):

monomer 1: Y-C_mH_2m-C_nF_2n+1(I)

Wherein m is an integer from 0 to 4, n is an integer from 1 to 12, and Y is an organic functional group selected from the following structures:

vinyl, halogen-substituted vinyl, alkyl-substituted vinyl; an acrylate group; c ═ C-O-C (O); or a methacrylate group; hydroxy, halogen; (C)_pH_2p+1O_q)3 Si-wherein p is an integer of 0 to 4 and q is an integer of 0 to 2.

As the buffer segment between the functional group Y and the perfluoroalkyl carbon chain, it is preferable that m is an integer of 0 to 2, in order to control the chain length within a suitable range, and to control the chain length too long, which will decrease the fluorine content of the whole molecule and is disadvantageous for improving the hydrophobic property.

In order to avoid the environment being burdened by the production of PFOA, PFOS, n is preferably an integer of 1 to 7.

As the substituent of the silane, p is preferably 1 or 2, and q is preferably 1.

Monomer 2:

R₁、R₂、R₃、R₄、R₅、R₆is independently selected from hydrogen, alkyl, aryl, halogenated aryl, halogen, halogenated alkyl, alkoxy and vinyl, and k is an integer of 0-4.

As the buffer segment of the unsaturated double bond and Si, k is preferably 0 to 2.

In order to further improve the compactness of the nano coating, a monomer 3 with a bifunctional structure is added:

R₇、R₈、R₉、R₁₀、R₁₁、R₁₂is independently selected from hydrogen, alkyl, aryl, halogen, halogenated alkyl and halogenated aryl. j. k is an integer of 0 to 10 and cannot be 0 at the same time. R₁₃Can be a bond, -CO-, -COO-, an aromatic subunit, an alicyclic alkyl subunit, or a hydroxyl-substituted aliphatic alkyl subunit. The monomer 3 may also be a multifunctional compound containing ester group, ether, epoxy group, cyano group. Preferred are glycidyl methacrylate, allyl glycidyl ether, 1, 2-epoxy-4-vinylcyclohexane, 3- (2, 3-glycidoxy) propylvinyldimethoxysilane, and enbuester.

It can be seen that, according to the embodiment of the present invention, the plasma source generates plasma to provide basic conditions for a reaction, in which the monomer 1, the monomer 2 and/or the monomer 3, which are one of the reaction raw materials, are added to a plasma atmosphere as a post-reaction raw material, in which the number of carbon atoms is relatively low, i.e., the waterproof nanomembrane is entirely formed of a compound having a relatively low number of carbon atoms, thereby preventing the generation of products polluting the environment from the viewpoint of raw materials. On the other hand, the fluorine content in the plasma source gas is high, so that the fluorine content in the deposited product, i.e., the water repellent nano-film is high, thereby compensating for the problem of poor hydrophobicity due to the decrease in the number of carbon atoms.

Further, according to an embodiment of the present invention, the preparation process of the waterproof nanomembrane may be: the preparation method comprises the steps of preparing a hydrophobic nano coating on the surface of a substrate by utilizing a PECVD (plasma enhanced chemical vapor deposition) process, placing the substrate in a vacuum or low-pressure reaction chamber, 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 substrate. The reactive raw material may be a chemical substance that is a gas at normal temperature and pressure, or may be a vapor formed by subjecting a liquid substance having a boiling point of less than 350 ℃ at normal pressure to a method such as pressure reduction and heating. In the deposition process, fluorocarbon gas is also introduced as a plasma source for generating plasma and stabilizing the plasma concentration balance in a reaction system.

According to an embodiment of the present invention, the overall preparation method of the waterproof nanomembrane may include the steps of:

1) substrate preparation

Before chemical vapor deposition, the substrate needs to be cleaned. Dust, moisture, grease, etc. on the surface of the substrate can adversely affect the deposition effect. The substrate is cleaned with acetone or isopropanol and then dried in a drying oven.

2) And carrying out chemical vapor deposition on the substrate to prepare the nano coating.

(1) Placing a substrate with a clean surface in a reaction chamber of a plasma device or equipment, continuously vacuumizing the reaction chamber, and vacuumizing the reaction chamber to 1-2000 mTorr;

(2) starting the movement mechanism to enable the substrate to be in a movement state in the cavity; introducing plasma source gas, and generating plasma in the cavity by means of radio frequency discharge or microwave, ultraviolet irradiation and the like. The monomer of the reaction raw material, such as monomer 1, monomer and/or monomer 3, can be introduced simultaneously with the plasma source, or the substrate can be pretreated for 1-1200 s after the plasma source is introduced, and then the reaction monomer is introduced according to the process parameter requirements. That is, in preparing the waterproof nanomembrane, the substrate is operated such that the substrate moves in a chamber of a PECVD apparatus, i.e., in a dynamic vapor deposition process. It is worth mentioning that the waterproof nanometer film formed on the surface of the substrate is more uniform and has stable performance in a mode that the substrate rotates in the cavity.

(3) Setting the pressure and the temperature of a vacuum reaction cavity, simultaneously introducing different monomers, regulating the plasma generation power to 1-500W, regulating the cavity temperature to 10-100 ℃, carrying out plasma chemical vapor deposition, stopping introducing the monomers after the reaction is finished, and increasing the cavity pressure to normal pressure.

Preferably, the plasma source gas is selected from carbon tetrafluoride, tetrafluoroethylene, hexafluoroethane.

The reactive raw materials, the monomer 1 and the monomer 2 can be mixed and introduced simultaneously or separately, or one of the two can be introduced selectively; the monomer 3 can be introduced or not introduced, or the monomer 3 is introduced first to deposit a first layer, and then the monomer 1 or the monomer 2 is introduced. When the monomer 3 and the monomer 1 or the monomer 2 are simultaneously introduced, the proportion of the monomer 3 is not higher than 30 percent.

The processed substrate can be an electronic product, a silk fabric, a woven bag, a metal surface, a glass surface, a ceramic surface and the like.

Further, preferably, the working power range of the plasma device is 30-200 w, and the pressure range is: 10 mTorr to 500 mTorr, temperature range is: 30-60 ℃.

The waterproof nanomembrane can be used to improve the waterproof or liquid-proof property of the substrate surface, that is, to make the substrate surface waterproof or liquid-proof, for example, the waterproof method of the substrate surface may be: exposing the substrate to a solution comprising the formula: c_xF_2x+2Or C_xF_2xAdding reaction raw materials into the plasma source atmosphere to carry out plasma enhanced chemical vapor deposition so as to form the waterproof nano film on the surface of the substrate, wherein x is 1,2 or 3.

The waterproof nanomembrane can be formed on a surface of a product to thereby post-process the product to enhance the waterproof or liquidproof properties of the surface or at least a portion of the surface of the product, such as, for example, a product having a waterproof nanomembrane by exposing the product to a composition comprising the structural formula: c_xF_2x+2Or C_xF_2xIs prepared by performing plasma enhanced chemical vapor deposition on reaction raw materials so that a waterproof nano film is formed on at least part of the surface of the product, wherein x is 1,2 or 3. The product is selected from: one of electronic products, silk fabrics, woven bags, metal products, glass products and ceramic products.