Hydrophobic and oleophobic coating layers, methods for manufacturing the same, and products

Abstract

The present invention discloses a hydrophobic / oleophobic coating layer, a method for producing the same, and a product, the hydrophobic / oleophobic coating layer being formed by growing perfluoropolyether or perfluoropolyether derivatives on the surface of a substrate by PECVD, and the perfluoropolyether or perfluoropolyether derivative coating layer improves the hydrophobic / oleophobic properties of the substrate surface. The present invention also discloses a hydrophobic / oleophobic coating layer, a method for producing the same, and a product, the hydrophobic / oleophobic coating layer having at least a two-layer structure, one layer being formed by plasma-enhanced chemical vapor deposition using one or more perfluoropolyethers or perfluoropolyether derivatives as raw materials, and the other layer being formed by plasma-enhanced chemical vapor deposition using a raw material containing silane or siloxane, thereby improving the hydrophobic / oleophobic properties of the substrate surface.

Description

[Technical Field]

[0001] [Cross reference] This application claims priority to the Chinese patent applications filed with the China National Intellectual Property Office on August 3, 2020, application number 202010766901.7, with the title of invention "Hydrophobic and oleophobic coating layer, method for manufacturing the same, and product," and filed with the China National Intellectual Property Office on August 3, 2020, application number 202010766907.4, with the title of invention "Hydrophobic and oleophobic coating layer, method for manufacturing the same, and product," the contents of which are incorporated into this application as a whole by reference.

[0002] This invention relates to the field of surface modification, and more particularly to hydrophobic and oleophobic coating layers formed by plasma chemical vapor deposition technology, methods for producing the same, and products thereof.

[0003] The present invention relates to the processing of fabric base materials, and more particularly to a hydrophobic and oleophobic coating layer formed by plasma chemical vapor deposition technology, a method for manufacturing the same, and a product thereof. The hydrophobic and oleophobic coating layer is suitable for improving the water-repellent and oil-repellent properties of the fabric base material. [Background technology]

[0004] Currently, hydrophobic and oleophobic products continue to be popular with consumers, and at the same time, research on hydrophobicity and oleophobicity is being reported one after another. Among these, the most studied compounds are perfluoro compounds (PFASs), which are widely used in industrial production due to their excellent thermal stability, hydrophobicity, and oleophobicity.

[0005] However, PFASs are difficult to decompose, easily bioaccumulate, and highly toxic, making them a new type of pollutant. Most of the decomposition products of PFASs are perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), which can cause damage to the reproductive, developmental, liver, and immune systems of animals, induce tumorigenesis, and have adverse effects on human health. Because these perfluoro compounds are difficult to decompose, many developed countries have issued bans on the use of perfluoro compounds containing long carbon chains, which undoubtedly limits the development and application of such hydrophobic and oleophobic coating layer technologies. How to achieve hydrophobic and oleophobic properties in fabrics while avoiding the environmental problems caused by the use of perfluoro compounds has become a hot topic of research in the field of hydrophobic and oleophobic coating layers in recent years.

[0006] The Chinese patent document with publication number CN107558184A discloses a method for producing hydrophobic and oleophobic agents for dough, the raw materials used in this method being non-toxic and harmless and not irritating to the human body. However, the synthesis process requires immersing the dough in reaction and stirring vessels, which can easily result in uneven impregnation and is not suitable for use in large-scale molded dough products.

[0007] Chinese patent document No. 2019105740043 discloses a fluorine-containing nanopolymer-modified nickel-titanium alloy material having superhydrophobic and oleophobic properties and a method for producing the same, and the surface of the modified nickel-titanium alloy material has excellent superhydrophobic and oleophobic properties. Chinese patent document No. 2018100098455 discloses a method for preparing superhydrophobic and oleophobic thin film materials by initial chemical vapor deposition, but these superhydrophobic and oleophobic materials utilize perfluoro compounds such as perfluoroacrylates and perfluorosiloxanes. This undoubtedly limits the development and application of such hydrophobic and oleophobic coating layer technology.

[0008] In recent years, the demand for hydrophobic and oleophobic materials has been increasing, and the hydrophobic and oleophobic properties of fabrics, in particular, are especially attractive to consumers. Textile materials treated with dual-repellent materials have a surface covered with a hydrophobic and oleophobic protective layer. This dual-repellent material can significantly reduce the surface free energy of the textile surface and significantly reduce the surface tension of the textile. When water or oil droplets adhere to the fabric, they form spherical droplets due to their own surface tension without wetting the material, creating a shield on the surface that can block various liquids and oil stains encountered in daily life. Textiles with hydrophobic and oleophobic properties have the potential to become a new fashion trend in textiles and bring significant economic and social benefits.

[0009] The Chinese patent, publication number CN1824884A, discloses a method for manufacturing a self-cleaning suit garment fabric having hydrophobic and oleophobic properties. In this invention, the surface of the garment fabric is first etched using low-temperature plasma technology to give the surface a certain electrostatic attraction, and then a hydrophobic and oleophobic material is adsorbed onto the surface of the garment fabric by immersion or spraying. This preparation method is very cumbersome, takes a long time to process, and is not suitable for mass or large-scale production.

[0010] Chinese patent application number 2018100098455 discloses the first method of preparing superhydrophobic and superoleophobic thin film materials using initiated chemical vapor deposition (CVD). This method combines conventional liquid-phase free radical polymerization with CVD technology, vaporizing the initiator and monomers necessary for polymerization and introducing them into a cavity. By decomposing the initiator at a relatively low heating temperature, the monomers are polymerized into a polymer thin film and grown on a substrate. Compared to conventional liquid-phase preparation processes, the thin films obtained by the CVD method are denser and more uniform, their thickness can be controlled, and they are suitable for substrates of all materials. This method requires the addition of a cryogenically decomposed initiator, and since most initiators require high temperatures for initiation, the use of initiators is limited. [Overview of the project]

[0011] The present invention is characterized by providing a hydrophobic / oil-repellent coating layer, a method for manufacturing the same, and a product, in which a hydrophobic / oil-repellent coating layer is formed on the surface of a substrate by a plasma-enhanced chemical vapor deposition method to improve the hydrophobic and oil-repellent properties of the substrate.

[0012] Another advantage of the present invention is to provide a hydrophobic / oil-repellent coating layer, a method for manufacturing the same, and a product, in which the raw material used for the hydrophobic / oil-repellent coating layer is a perfluoropolyether or a perfluoropolyether derivative.

[0013] Another advantage of the present invention is to provide a hydrophobic / oil-repellent coating layer, a method for manufacturing the same, and a product, in which the perfluoropolyether can include a K-type, Y-type, Z-type, or D-type structure.

[0014] Another advantage of the present invention is to provide a hydrophobic / oil-repellent coating layer, a method for manufacturing the same, and a product, in which the perfluoropolyether derivative can be a perfluoropolyether hydroxy derivative (PFPE-OH) having at least one hydroxy group.

[0015] Another advantage of the present invention is to provide a hydrophobic / oil-repellent coating layer, a method for manufacturing the same, and a product, in which the perfluoropolyether derivative can be an amorphous perfluorohomopolymer or copolymer of perfluorodioxole.

[0016] Another advantage of the present invention is to provide a hydrophobic / oil-repellent coating layer, a method for manufacturing the same, and a product, in which the raw material perfluoropolyether or perfluoropolyether derivative used is an environmentally friendly material that reduces environmental pollution.

[0017] To achieve at least one of the above advantages, one aspect of the present invention provides a hydrophobic and oleophobic coating layer, which includes forming the hydrophobic and oleophobic coating layer by growing a perfluoropolyether or a perfluoropolyether derivative on the surface of a substrate by PECVD.

[0018] In one embodiment, the hydrophobic and oleophobic coating layer comprises a perfluoropolyether structural formula including K-type, Y-type / Z-type, and D-type structures.

[0019] In the hydrophobic / oleophobic coating layer described in one embodiment, the molecular formula of the K-type is CF3CF2CF2O[CF(CF3)CF2O] n A hydrophobic and oleophobic coating layer of type CF(CF3)COF (where n is a natural number greater than or equal to 1).

[0020] In one embodiment, the hydrophobic and oleophobic coating layer has the following K-type structural formula. TIFF0007860076000001.tif3290 (where n is a natural number greater than or equal to 1.)

[0021] In the hydrophobic / oleophobic coating layer described in one embodiment, the Y-type molecular formula is CF3O(C3F6O) m (CF2O) n A hydrophobic and oleophobic coating layer, CF3 (where m is a natural number greater than or equal to 1, and n is a natural number greater than or equal to 1).

[0022] In one embodiment, the hydrophobic and oleophobic coating layer has the following Y-type structural formula. TIFF0007860076000002.tif1888 (where m is a natural number greater than or equal to 1, and n is a natural number greater than or equal to 1.)

[0023] In the hydrophobic / oleophobic coating layer described in one embodiment, the molecular formula of the Z-type is CF3O(C2F4O) m (CF2O)n A hydrophobic and oleophobic coating layer represented by CF3 (where m is a natural number of 1 or more and n is a natural number of 1 or more).

[0024] A hydrophobic and oleophobic coating layer in which the Z-type structural formula in one embodiment is as follows. JPEG0007860076000003.jpg1761 (where m is a natural number of 1 or more and n is a natural number of 1 or more).

[0025] In the hydrophobic and oleophobic coating layer described in one embodiment, the D-type molecular formula is C3F7O(CF2CF2CF2O) n A hydrophobic and oleophobic coating layer represented by C2F5 (where n is a natural number of 1 or more).

[0026] A hydrophobic and oleophobic coating layer in which the D-type molecular formula in one embodiment is as follows. TIFF0007860076000004.tif1796 (where n is a natural number of 1 or more).

[0027] In the hydrophobic and oleophobic coating layer described in one embodiment, the perfluoropolyether has the structural formula X1-O(CFXO) n (CFXCFXO) m (CF2CF2CF2O) p (CF2CF2CF2CF2O) q -X2(I) (where -X1 and X2 are independently selected from the structural formula -(CF2) Z CF3 and CF(CF3)COF (where z is an integer from 0 to 3), X is the same or different each time it appears and is independently F or CF3, n is an integer from 0 to 200, m is an integer from 0 to 200, p and q are integers from 0 to 100, p + q + m + n > 0, and the average molecular weight of (I) is between 200 and 10,000).

[0028] A hydrophobic and oleophobic coating layer according to one embodiment, wherein the perfluoropolyether derivative is a perfluoropolyether hydroxy derivative (PFPE-OH) having at least one hydroxyl group, and the derivative PFPE-OH corresponds to the chemical formula T1-O-Rf-T2 (wherein Rf is a fluoropolyoxyalkylene chain, and T1 and T2 are the same or different from each other and independently selected from the chemical formulas -CF2CH2O(CH2CH2O)s'H and -CF2CF2CH2O(CH2CH2O)s”H (wherein s' and s” are integers from 0 to 5)).

[0029] In the hydrophobic and oleophobic coating layer described in one embodiment, the fluoropolyoxyalkylene chain Rf of the derivative PFPE-OH is a repeating unit R ° A chain containing the repeating unit R ° (i)-CFXO- (where X is F or CF3), (ii)-CFXCFXO- (where X is the same or different F or CF3 in each instance, and the condition is that at least one X is -F), (iii)-CF2CF2CF2O-, (iv)-CF2CF2CF2CF2O-, (v)-(CF2) j A hydrophobic and oleophobic coating layer selected from -CFZ-O- (where j is an integer from 0 to 3, and Z is a group having the general formula -ORf'T3 (where Rf' is a fluoropolyoxyalkylene chain containing 0 to 10 repeating units, and T3 is a C1 to C3 perfluoroalkyl group)).

[0030] In the hydrophobic / oleophobic coating layer described in one embodiment, the repeating unit R in Rf' ° A hydrophobic and oleophobic coating layer, selected from -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, and -CF2CF2CF2CF2O-, where each X is independently F or CF3.

[0031] In a hydrophobic and oleophobic coating layer according to one embodiment, the perfluoropolyether or perfluoropolyether derivative is selected from SOLVAY's FLUOROLINK® MD700, FLUOROLINK® D, Fluorolink® E10H, Fluorolink® PEG45, Galden® SV55, Galden® HT170, Galden® SV80RP06, Fomblin® Y L-VAC16 / 6, Fomblin® Y, Fomblin® M100, or a mixture of multiple of the above products, in a hydrophobic and oleophobic coating layer.

[0032] A hydrophobic and oleophobic coating layer according to one embodiment, wherein the perfluoropolyether or perfluoropolyether derivative is 3M's Novec fluorinated solution, or is a mixture of one or more products containing perfluoropolyether or perfluoropolyether derivatives.

[0033] A hydrophobic and oleophobic coating layer according to one embodiment, wherein the perfluoropolyether derivative is a perfluoropolyether having at least one hydroxyl group, or a perfluoropolyether having at least one carboxyl group or ester group.

[0034] A hydrophobic and oleophobic coating layer according to one embodiment, wherein the vapor phase growth temperature is in the range of 30 to 60 degrees Celsius.

[0035] In other aspects, the present invention provides a method for producing a hydrophobic and oleophobic coating layer, which includes the step of using a perfluoropolyether or a perfluoropolyether derivative as a raw material and forming it by vapor phase growth on the surface of a substrate by PECVD.

[0036] A method for producing a hydrophobic and oleophobic coating layer according to one embodiment, wherein the perfluoropolyether derivative is a perfluoropolyether having at least one hydroxyl group, or a perfluoropolyether having at least one carboxyl group or ester group.

[0037] The present invention has the advantage of providing a hydrophobic and oleophobic coating layer, a method for manufacturing the same, and a product, in which a hydrophobic and oleophobic coating layer is formed on the surface of a substrate by plasma-enhanced chemical vapor deposition, and the hydrophobic and oleophobic coating layer is more suitable for improving the surface performance of the fabric.

[0038] Another advantage of the present invention is that it provides a hydrophobic and oleophobic coating layer, a method for manufacturing the same, and a product, which simplifies the process and reduces damage to the fabric by eliminating the need to immerse the fabric or etch the fabric surface when forming the hydrophobic and oleophobic coating layer on the surface of the fabric.

[0039] Another advantage of the present invention is that the hydrophobic and oleophobic coating layer is a multilayer composite coating layer, and the layer in contact with the fabric is formed by vapor phase growth of one or more silanes, siloxanes, or cyclosiloxanes to improve the hydrophobic performance of the substrate, as well as a method for producing the same and a product.

[0040] Another advantage of the present invention is that it provides a hydrophobic and oleophobic coating layer, a method for producing the same, and a product, in which another layer of the hydrophobic and oleophobic coating layer is formed by vapor phase growth of a perfluoropolyether or a perfluoropolyether derivative in order to improve the oleophobic performance of the substrate.

[0041] Another advantage of the present invention is that it provides a hydrophobic and oleophobic coating layer, a method for manufacturing the same, and a product, in which the hydrophobic and oleophobic coating layer is suitable for application to the surface of fabrics containing 70% or more nylon material, and is suitable for clothing fabrics containing 60% or more cotton material.

[0042] To achieve at least one of the above advantages, one aspect of the present invention provides a hydrophobic and oleophobic coating layer comprising at least two layers, one of which is formed by plasma vapor deposition using one or more perfluoropolyethers or perfluoropolyether derivatives as raw materials, and the other layer is formed by plasma vapor deposition using silane or siloxane as raw materials.

[0043] In one embodiment of the hydrophobic and oleophobic coating layer, the layer near the surface of the substrate is formed by the growth of a raw material containing silane or siloxane.

[0044] In a hydrophobic and oleophobic coating layer according to one embodiment, the outer layer is a hydrophobic and oleophobic coating layer formed by vapor phase growth using one or more perfluoropolyethers or perfluoropolyether derivatives as raw materials.

[0045] In the hydrophobic and oleophobic coating layer described in one embodiment, the raw materials containing silane or siloxane include vinyltrichlorosilane, 3-(methacryloyloxy)propyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-(2,3-glycidoxy)propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, vinyltriethoxysilane, and vinyltris(β-methoxyethoxy)silane. A hydrophobic and oleophobic coating layer selected from one or more mixtures of tetramethoxysilane, tetraethoxysilane, tetrapropyloxysilane, allyltrimethoxysilane, hexamethyldisiloxane, tetramethyldisiloxane, hexaethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, hexamethylcyclohexasiloxane, dodecamethylcyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethylcyclotrisiloxane, and hexadecylcyclooctasiloxane.

[0046] In a hydrophobic and oleophobic coating layer according to one embodiment, the perfluoropolyether or perfluoropolyether derivative is selected from one or more mixtures of SOLVAY's FLUOROLINK® MD700, FLUOROLINK® D, Fluorolink® E10H, Fluorolink® PEG45, Galden® SV55, Galden® HT170, Galden® SV80RP06, Fomblin® Y L-VAC16 / 6, Fomblin® Y, Fomblin® M100, and 3M's Novec fluorinated solution.

[0047] A hydrophobic and oleophobic coating layer according to one embodiment, wherein the hydrophobic and oleophobic coating layer is suitable for growing on the surface of a fabric material, and the fabric material is selected from nylon, polyester fiber, acrylic fiber, and cotton.

[0048] A hydrophobic and oleophobic coating layer according to one embodiment, wherein the hydrophobic and oleophobic coating layer is suitable for growing on the surface of a fabric containing 70% or more nylon material or on clothing fabric containing 60% or more cotton material.

[0049] A hydrophobic and oleophobic coating layer according to one embodiment, wherein the at least two-layer structure is formed by continuous growth multiple times during preparation.

[0050] In other aspects, the present invention provides a method for producing a hydrophobic and oleophobic coating layer, comprising the step of performing plasma vapor growth multiple times on the surface of a substrate to form at least two layers, wherein one layer is formed by plasma vapor growth using one or more perfluoropolyethers or perfluoropolyether derivatives as raw materials, and the other layer is formed by plasma vapor growth using raw materials containing silane or siloxane.

[0051] A method for producing a hydrophobic and oleophobic coating layer according to one embodiment, wherein the layer in contact with the surface of the substrate is formed by the growth of a raw material containing silane or siloxane.

[0052] A method for producing a hydrophobic and oleophobic coating layer according to one embodiment, wherein the outer layer is formed by vapor phase growth using one or more perfluoropolyethers or perfluoropolyether derivatives as raw materials. [Brief explanation of the drawing]

[0053] [Figure 1]Figure 1 is a schematic diagram of the test results of the water-repellent grade according to the first embodiment of the present invention. [Figure 2] Figure 2 is a schematic diagram of the test results of the oil-repellent grade according to the first embodiment of the present invention. [Figure 3] Figure 3 is a schematic diagram of the test results of the oil-repellent grade according to the second embodiment of the present invention. [Modes for carrying out the invention]

[0054] The following description is intended to disclose the invention so that those skilled in the art can achieve it. Preferred embodiments in the following description are illustrative only, and other obvious modifications are readily conceivable to those skilled in the art. The basic principles of the invention as defined in the following description can be applied to other embodiments, modifications, improvements, equivalents, and other technical modes that do not depart from the spirit and scope of the invention.

[0055] The term "1" should be understood as "at least one" or "one or more," meaning that in one embodiment, the number of elements may be one, but in another embodiment, the number of these elements may be multiple, and the term "1" should not be understood as a limitation on the number.

[0056] References such as "one embodiment," "embodiment," "exemplary embodiment," "various embodiments," and "several embodiments" indicate that such descriptions of embodiments of the present invention may include certain features, structures, or characteristics, but not all embodiments necessarily include those features, structures, or characteristics. Furthermore, some embodiments may have some, all, or none of the features described in other embodiments.

[0057] This invention discloses a hydrophobic and oleophobic coating layer that can be formed on the surface of a substrate by PECVD (Plasma Enhanced Chemical Vapor Deposition). The hydrophobic and oleophobic coating layer can improve the water-repellent and oil-repellent properties of the substrate surface.

[0058] Preferably, when preparing the hydrophobic / oleophobic coating layer, plasma vapor phase growth is performed using an inert gas as the gas source, such as argon gas or helium gas, but not limited to these. In other words, the inert gas is used as the pretreatment gas or plasma source gas.

[0059] Preferably, when preparing the hydrophobic / oleophobic coating layer, the power supply for the vacuum deposition film is a bias power supply, a high-frequency power supply, or a microwave power supply, and depending on the circumstances, a combination of two or three of the above may be used.

[0060] Preferably, when preparing the hydrophobic / oleophobic coating layer, the raw material used for the hydrophobic / oleophobic coating layer is a perfluoropolyether or a perfluoropolyether derivative.

[0061] Furthermore, the structural formulas of perfluoropolyethers include K-type, Y-type, Z-type, and D-type structures.

[0062] The molecular formula for the K-type is CF3CF2CF2O[CF(CF3)CF2O] n CF(CF3)COF The K-type structural formula is JPEG0007860076000005.jpg3075

[0063] The molecular formula for the Y type is CF3O(C3F6O). m (CF2O) n CF3 The Y-type structural formula is, TIFF0007860076000006.tif1880

[0064] The molecular formula for the Z-type is CF3O(C2F4O). m (CF2O) n CF3 The structural formula for Z-type is, JPEG0007860076000007.jpg2266

[0065] The molecular formula for type D is C3F7O(CF2CF2CF2O). n C2F5 The structural formula for type D is, TIFF0007860076000008.tif20102 (where m and n are both natural numbers greater than or equal to 1.)

[0066] The aforementioned perfluoropolyether has the following structural formula: X1-O(CFXO) n (CFXCFXO) m (CF2CF2CF2O) p (CF2CF2CF2CF2O) q -X2(I)(Here, -X1 and X2 are independent structural formulas -(CF2) Z It may also include having CF3 sum CF(CF3)COF (where z is an integer from 0 to 3), where X is the same or different each time it appears and is independently F or CF3, where n is an integer from 0 to 200, m is an integer from 0 to 200, p and q are integers from 0 to 100, where p+q+m+n>0, and the average molecular weight of (I) is between 200 and 10000.

[0067] Furthermore, the perfluoropolyether derivative is a perfluoropolyether hydroxy derivative (PFPE-OH) having at least one hydroxyl group, the PFPE-OH derivative having the chemical formula T1-O-Rf-T2 (where Rf is a fluoropolyoxyalkylene chain, and T1 and T2 are identical or different from each other and independently selected from the chemical formulas -CF2CH2O(CH2CH2O)s'H and -CF2CF2CH2O(CH2CH2O)s”H (where s' and s” are integers from 0 to 5)).

[0068] The fluoropolyoxyalkylene chain Rf of the derivative PFPE-OH is a repeating unit R ° A chain containing the repeating unit R ° teeth, (i)-CFXO-(where X is F or CF3), (ii)-CFXCFXO-(where X is the same or different F or CF3 each time it appears, and the condition is that at least one X is F.) (iii)-CF2CF2CF2O-, (iv)-CF2CF2CF2CF2O-, (v)-(CF2) j -CFZ-O- (where j is an integer from 0 to 3, and Z is a group having the general formula -ORf'T3 (where Rf' is a fluoropolyoxyalkylene chain containing 0 to 10 repeating units, the repeating units in Rf' being selected from -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O-, each X independently being F or CF3, and T3 being a C1-C3 perfluoroalkyl group).

[0069] Furthermore, the perfluoropolyether derivative may be an amorphous perfluorohopolymer or copolymer of perfluorodioxole. As shown in the structural formula, R'f is equal to RF or ORF, RF is a linear or branched perfluoroalkyl group containing 1 to 5 carbon atoms, X1 and X2 are the same or different, and F is CF3. TIFF0007860076000009.tif2726

[0070] Mono / dicarboxylic acid perfluoropolyethers having acid and / or ester functional groups are as shown in the structural formula AO-(RF) z -(CFY) t -C(O)OX (II), Here, X is H, C1~C 10 It is an alkyl group or an aryl group, Y=F, CF3, t=1, 2, or 3, A is a C1-C4 perfluoroalkyl terminal group or C(O)OX. z=0 or 1, and RF is a perfluoroalkylene chain containing one or more of the following units statistically distributed along the main chain: (C3F6O), (CFYO) (where Y is F or CF3), (CF2CF2O), (CF2CF2CF2CF2O), with a number-average molecular weight in the range of 180 to 8000.

[0071] Furthermore, the perfluoropolyether derivative may be a perfluoropolyether having at least one hydroxyl group, or a perfluoropolyether having at least one carboxyl group or ester group.

[0072] In particular, the hydrophobic and oleophobic coating layer is formed by growing a perfluoropolyether or a perfluoropolyether derivative on the surface of the substrate by low-temperature plasma chemical vapor deposition (CVM) to create a coating layer with hydrophobic and oleophobic properties. For example, the temperature range inside the cavity during chemical vapor deposition is 30 to 60 degrees Celsius, which is more suitable for protecting the substrate and avoiding damage to the substrate due to high temperatures.

[0073] In particular, the hydrophobic angle of the hydrophobic / oleophobic coating layer on glass products reaches 100 degrees or more, and the oleophobic angle of n-hexadecane is 60 degrees or more. It can be used as a hydrophobic / oleophobic layer or a fingerprint-resistant layer on glass, mobile phone screens, electronic products, medical devices, clothing fabrics, and textiles.

[0074] The reagents used for the above coating layer may be selected from SOLVAY's FLUOROLINK® MD700, FLUOROLINK® D, Fluorolink® E10H, Fluorolink® PEG45, Galden® SV55, Galden® HT170, Galden® SV80RP06, Fomblin® Y L-VAC16 / 6, Fomblin® Y, Fomblin® M100, or 3M's Novec fluorinating solutions, or a mixture of various products containing perfluoropolyether or perfluoropolyether derivatives.

[0075] According to embodiments of the present invention, the process for preparing the hydrophobic and oleophobic coating layer is as follows: (1) Place a substrate with a clean surface in the reaction cavity of a plasma apparatus, then continuously evacuate the reaction cavity to reduce the vacuum level in the reaction cavity to 1-200 mTorr, (2) Prepare a film layer by chemical vapor deposition of the substrate, (a) Introduce a plasma source gas (an inert gas such as helium or argon), start a pretreatment plasma discharge to pretreatment the substrate, generate plasma in the cavity by means of high-frequency discharge, microwave or pulse discharge, and introduce the monomer of the reaction raw material simultaneously with the plasma source gas, or, after the plasma source gas is introduced, pretreatment of the substrate for 1-1800 s before introducing the monomer of the reaction raw material according to the requirements of the process parameters. (b) Alternatively, the pressure and temperature in the vacuum reaction cavity may be set, gaseous or vaporized reaction material monomers may be introduced simultaneously, a growth plasma discharge may be started to perform plasma chemical vapor phase growth, the plasma generation power may be adjusted to 300-500 W and the cavity temperature to 30-60°C, and after the reaction is completed, the introduction of reaction material monomer gas may be stopped and the cavity pressure may be raised to atmospheric pressure. Particularly preferably, both the pretreatment plasma discharge and the growth plasma discharge are performed using a pulse bias power supply in constant power mode.

[0076] Furthermore, when preparing the hydrophobic and oleophobic coating layer, the process conditions used are as follows: A constant power mode pulse bias power supply is used for the discharge power supply, the plasma source gas flow rate is constant at 10-500 sccm, the pressure is constant at 10-200 mT, the monomer flow rate is 10-1000 ul / min, the deposition film power is 400-500 W, the frequency is 2 kHz-70 kHz, and the duty cycle is 5%-80%.

[0077] This invention discloses a hydrophobic and oleophobic coating layer that can be formed on the surface of a substrate by PECVD (Plasma Enhanced Chemical Vapor Deposition). The hydrophobic and oleophobic coating layer can improve the water-repellent and oil-repellent properties of the substrate surface.

[0078] Furthermore, the hydrophobic and oleophobic coating layer is suitable for improving the hydrophobic and oleophobic properties of the fabric surface, meaning that the substrate is preferably the fabric itself. The hydrophobic and oleophobic coating layer is grown on the surface of the fabric by PECVD, without the need for immersion treatment of the fabric or etching of the fabric surface, and protects the material properties of the fabric itself.

[0079] Furthermore, the hydrophobic and oleophobic coating layer is a composite coating layer including a multilayer structure. The hydrophobic and oleophobic coating layer includes at least a first layer and a second layer, the first layer being in close proximity to or in direct contact with the substrate, and the first and second layers are each formed by growth by PECVD.

[0080] Preferably, in one embodiment, the first layer is formed on the surface of a substrate, such as the surface of a fabric, by low-temperature plasma chemical vapor deposition from one or more silanes, siloxanes, or cyclosiloxanes. The second layer is formed by growing a perfluoropolyether or a perfluoropolyether derivative on the surface of the first layer. In other words, after forming the first layer by growing it on the surface of the substrate, the second layer is formed by continuing to grow, thereby obtaining the multilayer hydrophobic and oleophobic coating layer.

[0081] Preferably, the first and second layers of the multilayer hydrophobic / oleophobic coating layer are formed continuously in the same reactor, with each layer being grown under predetermined conditions. In some cases, in one embodiment, the first and second layers are formed intermittently in stages, that is, after one layer is grown, film layer performance is detected, and then the other layer is grown to obtain the multilayer structure. As can be seen from the test process, the continuous manufacturing process is superior to the intermittent manufacturing process. In other words, when preparing the multilayer hydrophobic / oleophobic coating layer, it is necessary to perform PECVD multiple times, and each PECVD process may be performed continuously in the same apparatus, or it may be performed in stages, with one layer being formed after another. Preferably, the multiple PECVD processes are performed continuously in the same apparatus, and after a pretreatment, reaction materials corresponding to different layers are introduced and the corresponding reaction conditions are controlled.

[0082] In particular, the first layer of the hydrophobic / oleophobic coating layer can improve the hydrophobicity of the substrate surface, and the second layer of the hydrophobic / oleophobic coating layer can improve the oleophobicity of the substrate surface, thereby giving the substrate good hydrophobicity and good oleophobicity.

[0083] Furthermore, when preparing the hydrophobic and oleophobic coating layer, plasma vapor phase growth is performed using an inert gas as a plasma source gas, although helium gas and argon gas are examples of such gases. Alternatively, helium gas or argon gas may be used as a plasma source gas, and helium gas or argon gas may be introduced in advance during growth to promote plasma generation in the reaction cavity.

[0084] Preferably, the hydrophobic and oleophobic coating layer is suitable for growing on the surface of a fabric including a woven, nonwoven, or knitted fabric base material, the fabric material being selected from one or more of nylon, polyester fibers, acrylic fibers, and cotton, and furthermore, the hydrophobic and oleophobic coating layer is suitable for growing on the surface of a fabric containing 70% or more nylon material, and on garment fabrics containing 60% or more cotton material.

[0085] Furthermore, when preparing the first layer, the silane or siloxane raw materials used include vinyltrichlorosilane, 3-(methacryloyloxy)propyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-(2,3-glycidoxy)propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, vinyltriethoxysilane, vinyltris(β-methoxy) It may be one or more of toxy)silane, tetramethoxysilane, tetraethoxysilane, tetrapropyloxysilane, allyltrimethoxysilane, hexamethyldisiloxane, tetramethyldisiloxane, hexaethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, hexamethylcyclohexasiloxane, dodecamethylcyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethylcyclotrisiloxane, or hexadecylcyclooctasiloxane.

[0086] When preparing the second layer of the hydrophobic / oleophobic coating layer, the perfluoropolyether or perfluoropolyether derivative raw material used is a mixture of one or more SOLVAY products: FLUOROLINK® MD700 (perfluoropolyether with ester groups), FLUOROLINK® D (perfluoropolyether with hydroxyl groups), Fluorolink® E10, Fluorolink® PEG45, Galden® SV55, Galden® HT170 (perfluoropolyether), Galden® SV80RP06, Fomblin® Y L-VAC16 / 6, Fomblin® Y, Fomblin® M100, or 3M's Novec fluorinated solution, or a mixture of monomers of multiple perfluoropolyethers or perfluoropolyether derivatives. The second layer, i.e., the outer layer, is the layer that comes into contact with the outside environment.

[0087] FLUOROLINK(registered trademark) D has the structural formula: HO-CH2CF2O(CF2O) m (CF2CF2O) n It has CF2CH2-OH (where m and n are integers).

[0088] Fluorolink (registered trademark) E10 has the structural formula: HO-(CH2CH2O) k CH2CF2O(CF2O) m (CF2CF2O) n cf2CH2(OCH2CH2) k -OH (where m and n are integers, and k=1, 2).

[0089] Galden® HT170 has the structural formula CF3O(CF2-CF(CF3)O). n (CF2O) m It contains CF3 (where n / m = 20) and has an average molecular weight of 450.

[0090] Fomblin® Y has the structural formula CF3O(C3F6O).n (CF2O) m It has CF3 (where n / m = 20).

[0091] According to embodiments of the present invention, the process for preparing the hydrophobic and oleophobic coating layer is as follows: (1) Place a substrate with a clean surface in the reaction cavity of a plasma apparatus, then continuously evacuate the reaction cavity to reduce the vacuum level in the reaction cavity to 1 to 2000 mTorr, (2) Prepare a film layer by chemical vapor deposition of the substrate, (a) Introduce a plasma source gas (an inert gas such as helium gas or argon gas), and use means such as high-frequency discharge, microwave or pulsed discharge in the cavity to generate plasma in the cavity and react The raw material monomers may be introduced simultaneously with the plasma source gas, or after introducing the plasma source gas, the substrate may be pretreated for 1 to 1800 seconds, and then the reaction raw material monomers may be introduced according to the requirements of the process parameters. (b) The pressure and temperature in the vacuum reaction cavity may be set, gaseous or vaporized reaction raw material monomers may be introduced simultaneously, the plasma generation power may be adjusted to 1 to 1000 W and the temperature in the cavity to 10 to 100 °C, plasma chemical vapor deposition may be performed, and after the reaction is completed, the introduction of reaction raw material monomers may be stopped and the cavity pressure may be raised to atmospheric pressure.

[0092] Furthermore, in one embodiment, the process conditions for preparing the hydrophobic and oleophobic coating layer are controlled as follows: 1. A pulse-biased power supply is used for the discharge power supply, with a maximum power of 12 kW. 2. The discharge power supply is in constant power mode, with a helium gas flow rate of 10-500 sccm, a constant pressure of 10-500 mT, a monomer flow rate of 10-1000 ul / min, a deposition film power of 100-1000 W, a frequency of 50 Hz-80 kHz, and a duty cycle of 5%-80%.

[0093] Preferably, the preparation process control conditions 1 during the growth of the first layer are as follows: A pulse-biased power supply in constant power mode is used as the discharge power supply, the plasma source gas flow rate is constant at 10-500 sccm, the pressure is constant at 10-500 mT, the monomer flow rate is 10-1000 ul / min, the deposition film power is 50W-600W, the frequency is 200Hz-80KHz, the duty cycle is 5-80%, the cavity temperature is 20-60°C, the evaporator temperature is 50-150°C, and the deposition film process time is 60 seconds-18000 seconds. In one embodiment, a pretreatment process can be performed before the plasma chemical growth of the first layer, that is, after the plasma source is introduced, the substrate is first pretreated by plasma discharge for 1-1800 seconds, and then the reaction material is introduced according to the requirements of the process parameters. The parameters for the pretreatment are as follows: The discharge power supply employs a pulse-biased power supply in constant power mode, with a plasma source gas flow rate of 10-500 sccm, a constant pressure of 10-200 mTorr, a deposition film power of 50W-600W, a frequency of 200Hz-80KHz, a duty cycle of 5%-80%, a cavity internal temperature of 20-60℃, and a pretreatment time of 1 second-1800 seconds.

[0094] Preferably, the preparation process control conditions 2 during the growth of the second layer are as follows: A pulse-biased power supply in constant power mode is used as the discharge power supply, the helium gas flow rate is constant at 10-500 sccm, the pressure is constant at 10-500 mT, the monomer flow rate is 10-1000 ul / min, the deposition film power is 50W-600W, the frequency is 200Hz-80KHz, the duty cycle is 5-80%, the cavity temperature is 20-60°C, and the evaporator temperature is 50-150°C. The deposition film process time is 60-18000 seconds. In one embodiment, a pretreatment process can be performed before the plasma chemical growth of the second layer; that is, after the plasma source is introduced, the substrate on which the first layer has been grown by plasma discharge is first pretreated for 1-1800 s, and then the reaction raw materials are introduced according to the requirements of the process parameters. The parameters for the pretreatment are as follows: The discharge power supply employs a pulse-biased power supply in constant power mode, with a plasma source gas flow rate of 10-500 sccm, a constant pressure of 10-200 mTorr, a deposition film power of 50W-600W, a frequency of 200Hz-80KHz, a duty cycle of 5%-80%, a cavity internal temperature of 20-60℃, and a pretreatment time of 1 second-1800 seconds.

[0095] Furthermore, the oil repellency test of the fabric measures the oil repellency of the fabric according to AATCC118 "Oil Drain: Hydrocarbon Resistance Test," and GB / T19977 and ISO14419 are essentially the same. Eight homologous solvents with gradually decreasing surface tension are used as standard solutions, and various grades of test solutions are dropped onto the prepared fabric surface, and the wetting of the fabric surface is observed after 30 seconds. If the test solution used last does not wet the fabric, this grade is the oil repellency grade of the tested fabric.

[0096] The water-repellency test of the fabric is performed according to AATCC22 "Detection and Evaluation of Water-Repellency of Textiles - Wetting Method," measuring the dynamic water repellency of the fabric. After water-repellent and oil-repellent treatment, the fabric sample is fixed to a metal ring with a diameter of approximately 150 mm and placed on a fixing frame tilted at a 45° angle. 250 mL of water is quickly poured from a glass funnel onto the sample, allowing natural spraying to be completed within 25-30 seconds. The fixing ring is removed, the fabric is turned downwards and lightly tapped horizontally, and the wetting of the sample surface is observed to evaluate its water-repellency value. [Examples]

[0097] Example 1 A glass wiped with alcohol was placed inside the reaction chamber of the plasma chamber, the reaction chamber was continuously evacuated to a vacuum of 20 mTorr, helium gas was introduced as the plasma source gas at a flow rate of 50 sccm, the internal temperature of the chamber was 55°C, and the plasma discharge was started to pre-treat the substrate. A pulse-biased power supply in constant power mode was used for the discharge power supply, with a power of 500 W, a pulse frequency of 50 kHz, a duty cycle of 10%, and a discharge time of 30 minutes.

[0098] Next, the monomer raw material was vaporized and then introduced into the reaction chamber. The internal temperature of the chamber was 45°C, the vaporization temperature of the monomer was 90°C, the helium gas flow rate was 50 sccm, the pressure was a constant 80 mTorr, the monomer flow rate was 350 ul / min, the film deposition stage was pulsed discharge, and a pulse-biased power supply in constant power mode was used for the discharge power supply, with a power of 400 W, a pulse frequency of 50 kHz, a duty cycle of 10%, and a discharge time of 160 seconds for the film deposition stage.

[0099] The monomer raw materials used were Fomblin® Y, FLUOROLINK® D, FLUOROLINK® MD700, Galden® HT170, and Japanese Fluorolink® PEG45 from SOLVAY. After the deposition film was completed, the hydrophobic angle was measured, and the oleophobic angle is shown in Table 1. The oleophobic angle was measured using n-hexadecane.

[0100] [Table 1]

[0101] Example 2 A nylon watch band was placed inside the reaction chamber of the plasma chamber, the reaction chamber was continuously evacuated to a vacuum of 20 mTorr, and helium gas was introduced as the plasma source gas at a flow rate of 50 sccm. The internal temperature of the chamber was 55°C, and plasma discharge was started to pre-treat the substrate. A pulse-biased power supply was used in constant power mode for the discharge power supply, with a power of 500 W, a pulse frequency of 50 kHz, a duty cycle of 10%, and a discharge time of 30 minutes.

[0102] Next, the monomer raw material Galden® HT170 was vaporized and then introduced into the reaction chamber. The internal temperature of the chamber was 50°C, the vaporization temperature of the monomer was 100°C, the helium gas flow rate was 50 sccm, the pressure was a constant 80 mTorr, the monomer flow rate was 300 ul / min, the film deposition stage was pulsed discharge, and a pulse bias power supply in constant power mode was used for the discharge power supply, with a power of 450 W, a pulse frequency of 50 kHz, a duty cycle of 20%, and a film deposition stage time of 160 seconds.

[0103] After the film deposition was completed, the hydrophobic angle was measured at 132°, and the oleophobic angle was measured at 93° with n-hexadecane.

[0104] Example 3 A glass wiped with alcohol was placed in a vacuum deposition chamber, and the reaction chamber was continuously evacuated to a vacuum of 80 mTorr. Helium gas was introduced as the plasma source gas at a flow rate of 50 sccm, the internal temperature of the chamber was 55°C, and the plasma discharge was started to pre-treat the substrate. A pulse-biased power supply in constant power mode was used for the discharge power supply, with a power of 500 W, a pulse frequency of 50 kHz, a duty cycle of 10%, and a discharge time of 30 minutes.

[0105] Next, a solution of the monomer raw materials, the bishydroxyperfluoropolyether derivative FLUOROLINK® D and the perfluoropolyether Galden® HT170, mixed in different mass ratios was mixed and vaporized. After vaporization, the solution was introduced into the reaction chamber. The internal temperature of the chamber was 45°C, the monomer vaporization temperature was 90°C, the helium gas flow rate was 50 sccm, the pressure was a constant 80 mTorr, the monomer flow rate was 400 ul / min, the film deposition stage was pulsed discharge, and the discharge power supply was a pulse-biased power supply in constant power mode with a power of 460 W, a pulse frequency of 50 kHz, a duty cycle of 20%, and the film deposition stage time was 160 seconds.

[0106] Different raw materials were mixed in the proportions shown in the table below. After the deposition of the film, the hydrophobic and oleophobic angles were measured and shown in Table 2. The oleophobic angle was measured using n-hexadecane.

[0107] [Table 2]

[0108] In particular, while glass and nylon watch bands were used as substrates in the above embodiments, other products or materials may be used as substrates in other embodiments. The multilayer composite film can be applied as a hydrophobic / oleophobic layer or an anti-fingerprint layer to various types of substrates with dense surface materials such as glass, mobile phone screens, electronic products, medical devices, clothing fabrics, and textiles, and the present invention is not limited in this respect.

[0109] Furthermore, in conventional technology, a film layer is formed on the surface of a substrate by immersing it in perfluoropolyether or a perfluoropolyether derivative, followed by heating and drying. This process is relatively complex and prone to damaging the substrate. However, in the proposed technology, a film layer is formed on the surface of a substrate by low-temperature vapor-phase growth of perfluoropolyether or a perfluoropolyether derivative using plasma vapor-phase growth technology. This simplifies the manufacturing process, protects the substrate, and maintains the good hydrophobic and oleophobic properties of the raw materials during film formation.

[0110] Example 4 A band-shaped material made of 70% nylon 66 was placed in the reaction chamber of the plasma chamber, and the reaction chamber was continuously evacuated to a vacuum of 80 mTorr. Helium gas was introduced at a flow rate of 50 sccm, and plasma discharge was started to pre-treat the substrate. The pre-treatment stage was pulsed discharge, and a pulse-biased power supply in constant power mode was used for the discharge power supply, with a power of 400 W, a pulse frequency of 50 kHz, a duty cycle of 10%, and a discharge time of 5 seconds.

[0111] Subsequently, hexamethylcyclohexasiloxane was vaporized and introduced into the reaction chamber. The pressure was kept constant at 80 mTorr, the monomer flow rate was 300 ul / min, the deposition stage was pulsed discharge, the power was 400 W, the pulse frequency was 50 kHz, the duty cycle was 10%, the internal chamber temperature was 55°C, the monomer vaporization temperature was 110°C, and the deposition process time was 320 seconds.

[0112] Subsequently, FLUOROLINK® D, purchased from SOLVAY, was vaporized and introduced into the reaction chamber. The pressure was kept constant at 80 mTorr, the monomer flow rate was 300 ul / min, the deposition stage was pulsed discharge, the power was 400 W, the pulse frequency was 50 kHz, the duty cycle was 10%, the internal chamber temperature was 50°C, the monomer vaporization temperature was 100°C, and the deposition process time was 160 seconds.

[0113] After the film deposition was complete, compressed air was filled into the chamber to return it to atmospheric pressure. The band-shaped material was removed, and the static hydrophobic angle, static oleophobic angle, water repellency, and oil repellency of the nylon band-shaped material were tested.

[0114] The test results for the water-repellent grade can be found in Figure 1, and the test results for the oil-repellent grade can be found in Figure 2. In Figure 2, 1- shows the test results for n-dodecane, 2- shows the test results for n-tetradecane, and 3- shows the test results for n-hexadecane. From Figure 1, when a static hydrophobic angle test was performed on nylon band-shaped materials, the material without a growing coating layer was clearly wet, but the material with a coating layer attached was not wet, and the water-repellent grade reached 5.

[0115] The static hydrophobic angle on the nylon band-like material was tested and found to be 143 degrees. The water-repellent performance of the nylon band-like material was also tested, and the test surface was dry with no water droplets, resulting in a water-repellent grade of 5.

[0116] The static oleophobicity angle on a nylon band-like material was tested. The static oleophobicity angle measured with n-hexadecane was 113 degrees, the oleophobicity angle measured with n-tetradecane was 104 degrees, and the oleophobicity angle measured with n-dodecane was 86 degrees, resulting in an oleophobicity grade of 4.

[0117] Example 5 A garment fabric made of polyester fiber material was placed in the reaction chamber of a plasma chamber, and a vapor deposition film was carried out using the method described in Example 4 above. After the vapor deposition film was completed, the garment fabric made of polyester fiber material was tested, and the static hydrophobic angle of the garment fabric made of polyester fiber material was measured to be 150 degrees.

[0118] The oleophobic angle of polyester fiber clothing fabric measured with olive oil was 120 degrees, the oleophobic angle measured with salad oil was 123 degrees, and the oleophobic angle measured with sunflower oil was also 123 degrees. Please refer to Figure 3, where 1-water, 2-olive oil, 3-salad oil, and 4-sunflower oil are shown.

[0119] The water-repellent and oil-repellent grades were tested using the above test method, and the water-repellent grade was 5, while the oil-repellent grade was 4.

[0120] Example 6 A cotton garment fabric was placed in the reaction chamber of the plasma chamber, and a vapor deposition film was carried out using the method described in Example 4 above. After the vapor deposition was completed, the cotton garment fabric was tested, and the static hydrophobic angle of the cotton garment fabric was measured to be 140 degrees, and the water repellency grade was 5. The static oleophobic angle measured with n-hexadecane was 111 degrees, the oleophobic angle measured with n-tetradecane was 100 degrees, and the oleophobic angle measured with n-dodecane was 83 degrees, with an oil repellency grade of 4.

[0121] Comparative Example of Example 4 Plan (1) Only the first layer of the coating layer was grown, using hexamethylcyclohexasiloxane as the raw material. A band-shaped material made of 70% nylon 66 was placed in the reaction chamber of the plasma chamber, and the reaction chamber was continuously evacuated to a vacuum of 80 mTorr. Helium gas was introduced at a flow rate of 50 sccm, and plasma discharge was started to pre-treat the substrate. The pre-treatment stage was pulse discharge, with a power of 400 W, a pulse frequency of 50 KHz, a duty cycle of 10%, and a discharge time of 5 seconds.

[0122] Subsequently, hexamethylcyclohexasiloxane was vaporized and introduced into the reaction chamber. The pressure was kept constant at 80 mTorr, the monomer flow rate was 300 ul / min, the deposition stage was pulsed discharge, the power was 400 W, the pulse frequency was 50 kHz, the duty cycle was 10%, the internal chamber temperature was 55°C, the monomer vaporization temperature was 110°C, and the deposition process time was 480 seconds.

[0123] After the vapor deposition was completed, the band-shaped material sample was tested. The static hydrophobic angle was 155 degrees, and the static oleophobic angle measured with n-hexadecane was 0 degrees. The water-repellent grade was 5, and the oleophobic grade was 0.

[0124] In the second method, only the second layer of the coating layer was grown. SOLVAY's FLUOROLINK® D was used as the raw material. A band-shaped material made of 70% nylon 66 was placed in the reaction chamber of the plasma chamber, and the reaction chamber was continuously evacuated to a vacuum of 80 mTorr. Helium gas was introduced at a flow rate of 50 sccm, and plasma discharge was started to pre-treat the substrate. The pre-treatment stage was pulse discharge, and a pulse bias power supply in constant power mode was used for the discharge power supply. The power was 400 W, the pulse frequency was 50 KHz, the duty cycle was 10%, and the discharge time was 5 seconds.

[0125] Subsequently, FLUOROLINK® D, purchased from SOLVAY, was vaporized and introduced into the reaction chamber. The pressure was kept constant at 80 mTorr, the monomer flow rate was 300 ul / min, the deposition stage was pulsed discharge, the power was 400 W, the pulse frequency was 50 kHz, the duty cycle was 10%, the internal chamber temperature was 50°C, the monomer vaporization temperature was 100°C, and the deposition process time was 480 seconds.

[0126] After the vapor deposition was completed, band-shaped material samples were tested. The measured static hydrophobic angle was 135 degrees, with a water-repellent grade of 3. The static oleophobic angle measured with n-hexadecane was 115 degrees, the oleophobic angle measured with n-tetradecane was 105 degrees, and the oleophobic angle measured with n-dodecane was 86 degrees, with an oleophobic grade of 4.

[0127] Comparative Example of Example 5 In the first method (1), only the first layer of the coating layer was grown, and raw material A was hexamethylcyclohexasiloxane. A garment fabric made of polyester fiber material was placed in the reaction chamber of the plasma chamber, and the reaction chamber was continuously evacuated to a vacuum of 80 mTorr. Helium gas was introduced at a flow rate of 50 sccm, and plasma discharge was started to pre-treat the substrate. The pre-treatment stage was pulse discharge, with a power of 400 W, a pulse frequency of 50 KHz, a duty cycle of 10%, and a discharge time of 5 seconds.

[0128] Subsequently, hexamethylcyclohexasiloxane was vaporized and introduced into the reaction chamber. The pressure was kept constant at 80 mTorr, the monomer flow rate was 300 ul / min, the deposition stage was pulsed discharge, the power was 400 W, the pulse frequency was 50 kHz, the duty cycle was 10%, the internal chamber temperature was 55°C, the monomer vaporization temperature was 110°C, and the deposition process time was 480 seconds.

[0129] After vapor deposition, the static hydrophobic angle of the clothing fabric was measured at 155 degrees, the oleophobic angle measured with olive oil was 0 degrees, the oleophobic angle measured with salad oil was 0 degrees, and the oleophobic angle measured with sunflower oil was 0 degrees. The water-repellent and oil-repellent grades were tested using the above test method, and the water-repellent grade was 5 and the oil-repellent grade was 0.

[0130] In the second method, only the second layer of the coating layer was grown. Raw material B was SOLVAY's FLUOROLINK® D. A polyester fiber garment fabric was placed in the reaction chamber of the plasma chamber, and the reaction chamber was continuously evacuated to a vacuum of 80 mTorr. Helium gas was introduced at a flow rate of 50 sccm, and the plasma discharge was started to pre-treat the substrate. The pre-treatment stage was pulsed discharge, and the discharge power supply was a pulse-biased power supply in constant power mode. The power was 400 W, the pulse frequency was 50 KHz, the duty cycle was 10%, and the discharge time was 5 seconds.

[0131] Subsequently, FLUOROLINK® D, purchased from SOLVAY, was vaporized and introduced into the reaction chamber. The pressure was kept constant at 80 mTorr, the monomer flow rate was 300 ul / min, the deposition stage was pulsed discharge, the power was 400 W, the pulse frequency was 50 kHz, the duty cycle was 10%, the internal chamber temperature was 50°C, the monomer vaporization temperature was 100°C, and the deposition process time was 480 seconds.

[0132] After the vapor deposition process was complete, the static hydrophobic angle of the polyester fiber garment fabric was measured at 140 degrees. The oleophobic angle measured with olive oil was 122 degrees, with salad oil it was 124 degrees, and with sunflower oil it was 124 degrees. The water-repellent and oil-repellent grades were tested using the above test method, and the water-repellent grade was 3 and the oil-repellent grade was 4.

[0133] Comparative Example of Example 6 In the first method (1), only the first layer of the coating layer was grown, and raw material A was hexamethylcyclohexasiloxane. Cotton clothing fabric was placed in the reaction chamber of the plasma chamber, and the reaction chamber was continuously evacuated to a vacuum of 80 mTorr. Helium gas was introduced at a flow rate of 50 sccm, and plasma discharge was started to pre-treat the substrate. The pre-treatment stage was pulse discharge, with a power of 400 W, a pulse frequency of 50 KHz, a duty cycle of 10%, and a discharge time of 5 seconds.

[0134] Subsequently, hexamethylcyclohexasiloxane was vaporized and introduced into the reaction chamber. The pressure was kept constant at 80 mTorr, the monomer flow rate was 300 ul / min, the deposition stage was pulsed discharge, the power was 400 W, the pulse frequency was 50 kHz, the duty cycle was 10%, the internal chamber temperature was 55°C, the monomer vaporization temperature was 110°C, and the deposition process time was 480 seconds.

[0135] After the vapor deposition was completed, the static hydrophobic angle of the garment fabric was measured at 145 degrees, and the static oleophobic angle measured with n-hexadecane was 0 degrees. The water-repellent and oil-repellent grades were tested using the above test method, and the water-repellent grade was 5, while the oil-repellent grade was 0.

[0136] In the second method, only the second layer of the coating layer was grown. Raw material B was SOLVAY's FLUOROLINK® D. Cotton clothing fabric was placed in the reaction chamber of the plasma chamber, and the reaction chamber was continuously evacuated to a vacuum of 80 mTorr. Helium gas was introduced at a flow rate of 50 sccm, and plasma discharge was started to pre-treat the substrate. The pre-treatment stage was pulsed discharge, and the discharge power supply was a pulse-biased power supply in constant power mode. The power was 400 W, the pulse frequency was 50 KHz, the duty cycle was 10%, and the discharge time was 5 seconds.

[0137] Subsequently, FLUOROLINK® D, purchased from SOLVAY, was vaporized and introduced into the reaction chamber. The pressure was kept constant at 80 mTorr, the monomer flow rate was 300 ul / min, the deposition stage was pulsed discharge, the power was 400 W, the pulse frequency was 50 kHz, the duty cycle was 10%, the internal chamber temperature was 50°C, the monomer vaporization temperature was 100°C, and the deposition process time was 480 seconds.

[0138] After the vapor deposition was completed, the static hydrophobic angle of the cotton garment fabric was measured to be 133 degrees. The static oleophobic angle measured with n-hexadecane was 113 degrees, the oleophobic angle measured with n-tetradecane was 101 degrees, and the oleophobic angle measured with n-dodecane was 85 degrees. The water-repellent and oil-repellent grades were tested using the above test method, and the water-repellent grade was 3 and the oil-repellent grade was 4.

[0139] Example 7 A band-shaped material made of 70% nylon 66 was placed in the reaction chamber of the plasma chamber, and the reaction chamber was continuously evacuated to a vacuum of 50 mTorr. Helium gas was introduced at a flow rate of 60 sccm, and plasma discharge was started to pre-treat the substrate. The pre-treatment stage was pulsed discharge, and a pulse-biased power supply in constant power mode was used for the discharge power supply, with a power of 400 W, a pulse frequency of 30 kHz, a duty cycle of 20%, and a discharge time of 30 seconds.

[0140] Subsequently, octamethylcyclotetrasiloxane was vaporized and introduced into the reaction chamber. The pressure was kept constant at 80 mTorr, the monomer flow rate was 300 ul / min, the deposition stage was pulsed discharge, the power was 400 W, the pulse frequency was 50 kHz, the duty cycle was 20%, the internal chamber temperature was 55°C, the monomer vaporization temperature was 110°C, and the deposition process time was 300 seconds.

[0141] Subsequently, Galden® HT170 purchased from SOLVAY was vaporized and introduced into the reaction chamber. The pressure was kept constant at 80 mTorr, the monomer flow rate was 300 ul / min, the deposition stage was pulsed discharge, the power was 400 W, the pulse frequency was 50 kHz, the duty cycle was 20%, the internal chamber temperature was 50°C, the monomer vaporization temperature was 100°C, and the deposition process time was 200 seconds.

[0142] After the film deposition was complete, compressed air was filled into the chamber to return it to atmospheric pressure. The band-shaped material was removed, and the static hydrophobic angle, static oleophobic angle, water repellency, and oil repellency of the nylon band-shaped material were tested.

[0143] The static hydrophobic angle on the nylon band-like material was tested and found to be 147 degrees. The water-repellent performance of the nylon band-like material was also tested, and the test surface was dry with no water droplets, resulting in a water-repellent grade of 5.

[0144] The static oleophobicity angle on a nylon band-like material was tested. The static oleophobicity angle measured with n-hexadecane was 115 degrees, the oleophobicity angle measured with n-tetradecane was 106 degrees, and the oleophobicity angle measured with n-dodecane was 87 degrees, resulting in an oleophobicity grade of 4.

[0145] Example 8 A cotton garment fabric was placed inside the reaction chamber of the plasma chamber, and the reaction chamber was continuously evacuated to a vacuum of 80 mTorr. Helium gas was introduced at a flow rate of 40 sccm, and plasma discharge was started to pre-treat the substrate. The pre-treatment stage was pulsed discharge, and a pulse-biased power supply in constant power mode was used. The power was 460 W, the pulse frequency was 30 kHz, the duty cycle was 30%, and the discharge time was 60 seconds.

[0146] Subsequently, tetramethoxysilane was vaporized and introduced into the reaction chamber. The pressure was kept constant at 80 mTorr, the monomer flow rate was 300 ul / min, the deposition stage was pulsed discharge, the power was 460 W, the pulse frequency was 50 kHz, the duty cycle was 30%, the internal chamber temperature was 55°C, the monomer vaporization temperature was 110°C, and the deposition process time was 300 seconds.

[0147] Subsequently, FLUOROLINK® D, purchased from SOLVAY, was vaporized and introduced into the reaction chamber. The pressure was kept constant at 80 mTorr, the monomer flow rate was 180 ul / min, the deposition stage was pulsed discharge, the power was 460 W, the pulse frequency was 50 kHz, the duty cycle was 30%, the internal chamber temperature was 55°C, the monomer vaporization temperature was 100°C, and the deposition process time was 500 seconds.

[0148] After the film deposition was complete, compressed air was filled into the chamber to return it to atmospheric pressure. The cotton garment fabric was removed, and its static hydrophobic angle, static oleophobic angle, water repellency, and oil repellency were tested.

[0149] The static hydrophobic angle of a cotton garment fabric was tested, and the static hydrophobic angle was 142 degrees. The water repellency performance of the cotton garment fabric was also tested, and the test surface was dry with no water droplets, resulting in a water repellency grade of 5.

[0150] The static oleophobicity angles of cotton clothing fabrics were tested. The static oleophobicity angles measured with n-hexadecane were 113 degrees, those measured with n-tetradecane were 104 degrees, and those measured with n-dodecane were 86 degrees, resulting in an oil repellency grade of 4.

[0151] Example 9 A garment fabric made of polyester fiber was placed in the reaction chamber of the plasma chamber, and the reaction chamber was continuously evacuated to a vacuum of 60 mTorr. Argon gas was introduced at a flow rate of 50 sccm, and plasma discharge was started to pre-treat the substrate. The pre-treatment stage involved pulse discharge, and a pulse-biased power supply in constant power mode was used for the discharge power, with a power of 500 W, a pulse frequency of 30 kHz, a duty cycle of 15%, and a discharge time of 30 seconds.

[0152] Subsequently, hexamethyldisiloxane was vaporized and introduced into the reaction chamber. The pressure was kept constant at 60 mTorr, the monomer flow rate was 300 ul / min, the deposition stage was pulsed discharge, the power was 500 W, the pulse frequency was 50 kHz, the duty cycle was 15%, the internal chamber temperature was 55°C, the monomer vaporization temperature was 110°C, and the deposition process time was 300 seconds.

[0153] Subsequently, FLUOROLINK® D, purchased from SOLVAY, was vaporized and introduced into the reaction chamber. The pressure was kept constant at 60 mTorr, the monomer flow rate was 180 ul / min, the deposition stage was pulsed discharge, the power was 500 W, the pulse frequency was 50 kHz, the duty cycle was 15%, the internal chamber temperature was 55°C, the monomer vaporization temperature was 110°C, and the deposition process time was 300 seconds.

[0154] After the film deposition was complete, compressed air was filled into the chamber to return it to atmospheric pressure. The polyester fiber garment fabric was removed, and its static hydrophobic angle, static oleophobic angle, water repellency, and oil repellency were tested.

[0155] The static hydrophobic angle of the polyester fiber garment fabric was tested, and the static hydrophobic angle was 142 degrees. The water repellency performance of the polyester fiber garment fabric was also tested, and the test surface was dry with no water droplets, and the water repellency grade was 5.

[0156] The static oleophobicity angles of clothing fabrics made of polyester fibers were tested. The static oleophobicity angles measured with n-hexadecane were 116 degrees, those measured with n-tetradecane were 107 degrees, and those measured with n-dodecane were 87 degrees, resulting in an oil repellency grade of 4.

[0157] Example 10 A band-shaped material made of nylon 66 was placed in the reaction chamber of the plasma chamber, and the reaction chamber was continuously evacuated to a vacuum of 80 mTorr. Helium gas was introduced at a flow rate of 50 sccm, and plasma discharge was started to pre-treat the substrate. The pre-treatment stage involved pulse discharge, and a pulse-biased power supply in constant power mode was used for the discharge power, with a power of 500 W, a pulse frequency of 30 kHz, a duty cycle of 10%, and a discharge time of 100 seconds.

[0158] Subsequently, 3-(methacryloyloxy)propyltrimethoxysilane was vaporized and introduced into the reaction chamber. The pressure was kept constant at 80 mTorr, the monomer flow rate was 350 ul / min, the deposition stage was pulsed discharge, the power was 500 W, the pulse frequency was 30 kHz, the duty cycle was 10%, the internal chamber temperature was 55°C, the monomer vaporization temperature was 110°C, and the deposition process time was 300 seconds.

[0159] Subsequently, Fomblin® Y, purchased from SOLVAY, was vaporized and introduced into the reaction chamber. The pressure was kept constant at 80 mTorr, the monomer flow rate was 350 ul / min, the deposition stage was pulsed discharge, the power was 500 W, the pulse frequency was 30 kHz, the duty cycle was 10%, the internal chamber temperature was 55°C, the monomer vaporization temperature was 110°C, and the deposition process time was 300 seconds.

[0160] After the film deposition was complete, compressed air was filled into the chamber to return it to atmospheric pressure. The band-shaped material was removed, and the static hydrophobic angle, static oleophobic angle, water repellency, and oil repellency of the nylon band-shaped material were tested.

[0161] The static hydrophobic angle on the nylon band-like material was tested, and the static hydrophobic angle was 140 degrees. The water-repellent performance of the nylon band-like material was also tested, and the test surface was dry with no water droplets, and the water-repellent grade was 5.

[0162] The static oleophobicity angle on a nylon band-like material was tested. The static oleophobicity angle measured with n-hexadecane was 108 degrees, the oleophobicity angle measured with n-tetradecane was 100 degrees, and the oleophobicity angle measured with n-dodecane was 83 degrees, resulting in an oleophobicity grade of 4.

[0163] Those skilled in the art should understand that the embodiments of the present invention shown in the above description and accompanying drawings are merely examples and do not limit the present invention. The object of the present invention has already been fully and effectively achieved. The functional and structural principles of the present invention are also shown in the embodiments, and any changes or modifications can be made to the embodiments of the present invention without departing from the said principles.

Claims

1. Formed by growing a perfluoropolyether derivative or a mixture of perfluoropolyether and perfluoropolyether derivatives on the surface of a substrate using PECVD, The perfluoropolyether derivative has the chemical formula T 1 -O-Rf-T 2 where Rf is a fluoropolyoxyalkylene chain, and T 1 and T 2 are the same as or different from each other and independently have the chemical formula -CF 2 CH 2 O(CH 2 CH 2 O) s ’H and -CF 2 CF 2 CH 2 O(CH 2 CH 2 O) s ​ The fluoropolyoxyalkylene chain Rf of the perfluoropolyether derivative is a chain containing repeating units R°, where the repeating units R° are (i) -CFXO- (where X is F or CF3), (ii) -CFXCFXO- (where X is the same or different F or CF3 each time it appears, and conditionally at least one X is -F), (iii) -CF2CF2CF2O-, (iv) -CF2CF2CF2CF2O-, (v) -(CF2)j-CFZ-O- (where j is an integer from 0 to 3, and Z is the general formula -ORf'T3 (where Rf' is a fluoropolyoxyalkylene chain containing 0 to 10 repeating units, and T3 is C1 to C3) It is a perfluoroalkyl group.) It is a group having ), selected from ), and the repeating unit in Rf' is selected from a group consisting of -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O-, where each X is independently F or CF3, The perfluoropolyether is a hydrophobic and oleophobic coating layer having the chemical formula X1 -O(CFXO)n (CFXCFXO)m (CF2CF2CF2O)p (CF2CF2CF2CF2O)q -X2(I) (where -X1 and X2 are independently selected from the structural formulas -(CF2)ZCF3 and CF(CF3)COF (where z is an integer from 0 to 3), X is the same or different each time it appears and is independently F or CF3, n is an integer from 0 to 200, m is an integer from 0 to 200, p and q are integers from 0 to 100, p+q+m+n>0, and the average molecular weight of (I) is between 200 and 10000).

2. The hydrophobic and oleophobic coating layer according to claim 1, wherein the vapor phase growth temperature is in the range of 30 to 60 degrees Celsius.

3. The method is characterized by using a perfluoropolyether derivative or a mixture of perfluoropolyether and perfluoropolyether derivatives as a raw material and forming it on the surface of a substrate by PECVD. Perfluoropolyether derivatives have the chemical formula T 1 -O-Rf-T 2 (Here, Rf is a fluoropolyoxyalkylene chain, T 1 and T 2 They are either identical or different from each other, and independently have the chemical formula -CF 2 CH 2 O(CH 2 CH 2 O) s 'H and -CF 2 CF 2 CH 2 O(CH 2 CH 2 O) s It has "H (where s' and s'' are integers from 0 to 5)", The fluoropolyoxyalkylene chain Rf of the perfluoropolyether derivative is a chain containing repeating units R°, where the repeating units R° are (i) -CFXO- (where X is F or CF3), (ii) -CFXCFXO- (where X is the same or different F or CF3 each time it appears, and conditionally at least one X is -F), (iii) -CF2CF2CF2O-, (iv) -CF2CF2CF2CF2O-, (v) -(CF2)j-CFZ-O- (where j is an integer from 0 to 3, and Z is the general formula -ORf'T3 (where Rf' is a fluoropolyoxyalkylene chain containing 0 to 10 repeating units, and T3 is C1 to C3) It is a perfluoroalkyl group.) It is a group having ), selected from ), and the repeating unit in Rf' is selected from a group consisting of -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O-, where each X is independently F or CF3, A method for producing a hydrophobic and oleophobic coating layer, wherein the perfluoropolyether has the chemical formula X1 -O(CFXO)n (CFXCFXO)m (CF2CF2CF2O)p (CF2CF2CF2CF2O)q -X2(I) (where -X1 and X2 are independently selected from the structural formulas -(CF2)ZCF3 and CF(CF3)COF (where z is an integer from 0 to 3), X is the same or different each time it appears and is independently F or CF3, n is an integer from 0 to 200, m is an integer from 0 to 200, p and q are integers from 0 to 100, p+q+m+n>0, and the average molecular weight of (I) is between 200 and 10000).

4. The method for producing a hydrophobic and oleophobic coating layer according to claim 3, wherein the preparation process for the hydrophobic and oleophobic coating layer is as follows: (1) a substrate is placed in the reaction cavity of a plasma chamber, and the vacuum in the reaction cavity is evacuated to 10 to 200 mTorr; (2) a plasma source gas is introduced and a pretreatment plasma discharge is started to pretreat the substrate; (3) after vaporizing the reaction raw material monomer, it is introduced into the reaction cavity, and a growth plasma discharge is started to carry out a chemical vapor phase growth reaction; and (4) the growth plasma discharge is stopped, compressed air or an inert gas is introduced to return to atmospheric pressure, the cavity is opened, and the substrate is removed.

5. The method for producing a hydrophobic and oleophobic coating layer according to claim 4, wherein the reaction raw material monomer is introduced simultaneously with the plasma source gas, or the substrate is pre-treated for 1 to 1800 s after the introduction of the plasma source gas, and then the reaction raw material monomer is introduced.

6. The method for manufacturing a hydrophobic and oleophobic coating layer according to claim 4, wherein both the pretreatment plasma discharge and the growth plasma discharge are performed using a pulse-biased power supply in constant power mode.

7. It comprises at least two layers, the outer layer being formed by plasma chemical vapor deposition using a perfluoropolyether derivative or a mixture of perfluoropolyether and perfluoropolyether derivatives as raw materials, and the other layer being formed by plasma chemical vapor deposition using a raw material containing silane or siloxane. Perfluoropolyether derivatives have the chemical formula T 1 -O-Rf-T 2 (Here, Rf is a fluoropolyoxyalkylene chain, T 1 and T 2 They are either identical or different from each other, and independently have the chemical formula -CF 2 CH 2 O(CH 2 CH 2 O) s 'H and -CF 2 CF 2 CH 2 O(CH 2 CH 2 O) s It has "H (where s' and s'' are integers from 0 to 5)", The fluoropolyoxyalkylene chain Rf of the perfluoropolyether derivative is a chain containing repeating units R°, where the repeating units R° are (i) -CFXO- (where X is F or CF3), (ii) -CFXCFXO- (where X is the same or different F or CF3 each time it appears, and conditionally at least one X is -F), (iii) -CF2CF2CF2O-, (iv) -CF2CF2CF2CF2O-, (v) -(CF2)j-CFZ-O- (where j is an integer from 0 to 3, and Z is the general formula -ORf'T3 (where Rf' is a fluoropolyoxyalkylene chain containing 0 to 10 repeating units, and T3 is C1 to C3) It is a perfluoroalkyl group.) It is a group having ), selected from ), and the repeating unit in Rf' is selected from a group consisting of -CFXO-, -CF2CFXO-, -CF2CF2CF2O-, -CF2CF2CF2CF2O-, where each X is independently F or CF3, The perfluoropolyether is a hydrophobic and oleophobic coating layer having the chemical formula X1 -O(CFXO)n (CFXCFXO)m (CF2CF2CF2O)p (CF2CF2CF2CF2O)q -X2(I) (where -X1 and X2 are independently selected from the structural formulas -(CF2)ZCF3 and CF(CF3)COF (where z is an integer from 0 to 3), X is the same or different each time it appears and is independently F or CF3, n is an integer from 0 to 200, m is an integer from 0 to 200, p and q are integers from 0 to 100, p+q+m+n>0, and the average molecular weight of (I) is between 200 and 10000).

8. The hydrophobic and oleophobic coating layer according to claim 7, wherein the layer near the surface of the substrate is formed by the growth of a raw material containing silane or siloxane.

9. Raw materials containing silane or siloxane include vinyltrichlorosilane, 3-(methacryloyloxy)propyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-(2,3-glycidoxy)propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, tetramethoxysilane, tetraeth A hydrophobic and oleophobic coating layer according to claim 7, selected from one or more mixtures of xysilane, tetrapropyloxysilane, allyltrimethoxysilane, hexamethyldisiloxane, tetramethyldisiloxane, hexaethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, hexamethylcyclohexasiloxane, dodecamethylcyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethylcyclotrisiloxane, and hexadecylcyclooctasiloxane.

10. The hydrophobic and oleophobic coating layer according to claim 7, wherein the hydrophobic and oleophobic coating layer is suitable for growing on the surface of the fabric material, and the fabric material is selected from nylon, polyester fibers, acrylic fibers, and cotton.

11. The hydrophobic and oleophobic coating layer according to claim 7 is suitable for growing on the surface of a fabric containing 70% or more nylon material or on clothing fabric containing 60% or more cotton material.

12. The hydrophobic and oleophobic coating layer according to claim 7, wherein the at least two layers are formed by growing multiple times consecutively during preparation, with one layer being formed during each growth.

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