Formulations and methods for producing repellent surfaces - Patents.com

Abstract

An all-in-one formulation for preparing a repellent coating on a surface of a substrate includes (i) one or more reactive components capable of forming a bonding layer on the surface, the bonding layer comprising an array of compounds having one end bonded to the surface and another end extending away from the surface, (ii) an optional catalyst, (iii) a solvent, and (iv) a lubricant. A repellent coating can be formed from such a formulation on a substrate surface by drying the formulation on the surface to substantially remove the solvent and form a bonding layer on the surface with the lubricant stably attached to the bonding layer. The formulation can be applied to ceramic, glass, metal, alloy, composite, polymer, or a combination thereof, such as the surface of ceramic or metal sanitary appliances, surfaces of glass substrates including mirrors, windshields, and windows, surfaces composed of one or more polymers, medical devices such as ostomy appliances, and the like.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application No. 62 / 900,207, filed September 13, 2019, U.S. Provisional Patent Application No. 62 / 935,887, filed November 15, 2019, and U.S. Provisional Patent Application No. 62 / 992,589, filed March 20, 2020, the entire disclosures of each of which are hereby incorporated by reference herein.

[0002] The present invention relates to formulations and their use for forming repellent coatings on the surfaces of substrates, including the surfaces of medical devices. [Background technology]

[0003] Several patent applications disclose repellent and anti-biofouling surfaces, including, for example, WO 2019 / 222007, US 2019 / 0016903, and WO 2018094161 to Wong et al., WO 2013106588 to Ingber et al., and US 2018 / 0187022 to Aizenberg et al. The paper by Wang et al. also discloses repellent surfaces created with modified surfaces for fluid and solid repellency. See Wang et al. Covalently Attached Liquids: Instant Omniphobic Surfaces with Unprecedented Repellency. Angewandte Chemie International Edition 55, 244-248 (2016). Summary of the Invention

[0004] However, developing a simple, scalable method for creating slippery surfaces on a wide variety of substrate materials remains a challenge.

[0005] The advantages of the present disclosure include formulations and methods for preparing repellent coatings for a wide range of solid surfaces, including those composed of one or more polymers, ceramics, glasses, metals, alloys, composites, or combinations thereof. The formulations of the present disclosure can include reactive components and lubricants together in a single formulation (all-in-one formulation), and can advantageously be used to create repellent coated surfaces by a simple one-step method. The repellent coatings can be formed on a wide variety of surfaces, such as ceramic or metal sanitary utensils and devices, glass substrates including mirrors, windshields, windows, medical devices such as stoma appliances, and the like. The formed repellent coatings are slippery and can repel and reduce adhesion to liquids, bacteria, mineral deposits, ice, frost, and viscoelastic materials (e.g., viscoelastic semi-solids and solids).

[0006] These and other advantages are met, at least in part, by a formulation that includes (i) one or more reactive components capable of forming a bonding layer on a surface, said bonding layer comprising an array of compounds having one end bonded to the surface and another end extending away from the surface, (ii) an optional catalyst, (iii) a solvent, and (iv) a lubricant.

[0007] In some embodiments, the formulations of the present disclosure may include low molecular weight silanes or siloxanes, e.g., having one or more hydrolyzable groups. Such silanes or siloxanes may have a molecular weight of less than about 1,500 g / mol, e.g., less than about 1,000 g / mol, and may include, e.g., alkoxysilanes, dialkoxysilanes, trialkoxysilanes, or combinations thereof. In certain embodiments, the array of compounds and / or polymers formed from the reactive compounds are not crosslinked along their chains. In still further embodiments, the relative amount by weight of the one or more reactive components to the lubricant in the formulation includes 1 part reactive component to about 0.01 to about 1 part lubricant. The catalyst may include an acid catalyst, e.g., sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid, or combinations thereof. The solvent may include lower ketones, lower alcohols, lower ethers, lower esters, lower halogenated solvents, and combinations thereof. The lubricant may include silicone oils or mineral oils or vegetable oils, or any combinations thereof. Other ingredients, such as fragrances, may be included in the formulations of the present disclosure.

[0008] A further advantage of the present disclosure includes a method of forming a repellent coating on a surface from the formulation disclosed herein. The method includes drying the formulation disclosed herein on the surface of a substrate to substantially remove the solvent and form a bonding layer on the surface with the lubricant stably attached to the bonding layer. Advantageously, the formed bonding layer includes an array of compounds having one end bonded to the surface and another end extending away from said surface. The method can also include applying the formulation to the substrate surface before drying the formulation on the surface. Such a method can avoid multiple steps of forming a repellent coating, such as first forming a bonding layer and then applying a lubricant layer to the preformed bonding layer.

[0009] In some embodiments, the method of forming a repellent coating on a substrate from the formulation disclosed herein comprises drying the formulation on the glass, ceramic or polymer surface of the substrate to substantially remove the solvent and form a bonding layer on the surface with the lubricant stably attached to the bonding layer.One or more reactive components can be covalently bonded to the surface to form an array of compounds having one end bonded to the surface and the other end extending away from the surface to form a bonding layer.Repellent coatings can be formed on a wide variety of surfaces, such as ceramic or metal sanitary utensils and devices, glass substrates including mirrors, windshields, windows, medical devices such as stoma appliances, and the like.

[0010] The method of the present disclosure may further comprise forming a coupling layer on the substrate surface, for example the substrate surface composed of one or more polymers, to couple the repellent coating to the substrate surface. Such coupling layer comprises functional groups, for example hydroxyl, ester, or acidic side groups, which can react with the reactive components of the formulation of the present disclosure.

[0011] The method of the present disclosure may further comprise applying the formulation to the surface of the substrate. Advantageously, the application and / or drying of the formulation may be carried out in air and / or at atmospheric pressure.

[0012] In some embodiments, a formulation that is applied to a surface of a substrate to form a repellent coating thereon can include (i) one or more reactive components; (ii) an acid catalyst; (ii) a solvent; and (iv) a lubricant having a viscosity of from 2 cSt to 1000 cSt measured at 25° C.

[0013] Another advantage of the present disclosure includes a substrate having a repellent coating thereon. Such substrates can include those composed of one or more polymers, ceramics, glass, metals, alloys, composites or combinations thereof. The repellent coating of the present disclosure can be formed on medical devices, including medical devices having a surface composed of one or more polymeric components, such as on one or more surfaces of stoma appliances. Advantageously, the repellent coating comprises a bonding layer on the surface of the substrate, comprising an array of compounds having one end bonded to the surface and the other end extending away from the surface.

[0014] Further advantages of the present invention will become readily apparent to those skilled in the art from the following detailed description, in which only preferred embodiments of the invention are shown and described, merely by way of illustration of the best mode contemplated for carrying out the invention. As will be realized, the invention is capable of other and different embodiments, and its several details are capable of modification in various obvious respects, all without departing from the invention. Accordingly, the drawings and description should be regarded as illustrative in nature, and not restrictive.

[0015] Reference is made to the accompanying drawings, in which elements having the same reference numeral designations represent like elements throughout. [Brief description of the drawings]

[0016] [Figure 1] FIG. 1 is a schematic diagram of the preparation of a repellent coating according to the present disclosure. [Diagram 2] FIG. 1 is a schematic diagram of the preparation of a repellent surface on a substrate having a reactive coupling layer. [Diagram 3] 1 is a graph showing water sliding angle versus lubricant concentration for formulations containing the concentrations of lubricant used to form a repellent coating according to the present disclosure. The volume of the water droplets used was 20 μL. [Figure 4] 1 is a graph showing water sliding angle versus the ratio of lubricant to reactive components in the formulation used to prepare the repellent coating. The volume of the water droplet used was 20 μL. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The present disclosure relates to a formulation that can greatly simplify and reduce the manufacturing time, number of steps, and cost associated with forming a repellent coating system. The repellent coating system that can be formed by the formulation of the present disclosure includes a system of a lubricant layer infused into a bonding layer. Typically, the preparation of such a repellent coating system required separate steps consisting of preparing one or more layers to be bonded to a surface, followed by washing the formed bonding layer, and then applying a lubricant layer to the washed bonding layer. It was not anticipated that an all-in-one formulation could be used to prepare a repellent coating system that includes a bonding layer with an infused lubricant layer, assuming that the lubricant may interfere with the reactive components that form the bonding layer, or that the lubricant does not properly form the infused layer with the bonding layer. It was further not anticipated that the conventional practice of washing the formed bonding layer before applying the lubricant could be avoided. However, the formulation of the present disclosure can advantageously form a repellent coating system of a lubricant layer stably attached in a bonding layer by using a single formulation that includes the components to completely form the repellent coating system without the need for separate steps.

[0018] Such formulations include (i) reactive components for forming a bonding layer on the surface of the substrate, (ii) an optional catalyst, (iii) a solvent, and (iv) a lubricant. The reactive components of the formulation are used to form a bonding layer on the surface of the substrate by reacting with the surface to allow the formation of an array of compounds on the surface having one end covalently bonded to the surface and the other end extending away from said surface. The bonding layer thus resembles a brush, with linear chains attached to the surface. The lubricant of the formulation stably attaches to the bonding layer primarily via van der Waals interactions, forming a repellent coating system (hereinafter referred to as a repellent coating) on ​​the surface. The catalyst can facilitate and accelerate the formation of the bonding layer in a shorter time and at a reduced temperature, and the solvent can also facilitate the formation of the bonding layer and the immobilization of the lubricant within the bonding layer.

[0019] The bonding layer can be formed directly or indirectly on the surface of the substrate by reacting the reactive components of the formulation with functional groups, such as hydroxyl groups, acid groups, ester groups, etc., on the surface of the substrate. Such functional groups can be naturally present or can be induced on the substrate, such as by treating the surface with oxygen plasma or by heating in the presence of air or oxygen. A coupling layer can be formed on the substrate surface, such as a substrate surface composed of one or more polymers, to couple the repellent coating to the substrate surface. Such coupling layers contain functional groups, such as hydroxyl, ester or acidic side groups, which can react with the reactive components of the formulations of the present disclosure and include, for example, silica or silicon dioxide layers, metal oxide layers, such as titanium dioxide, aluminum oxide, polymer layers having hydroxyl, ester or acidic side groups, such as poly(vinyl alcohol) (PVA) or copolymers thereof, poly(vinyl acetate) (PVAc) or copolymers thereof, such as poly(ethylene vinyl acetate) (PEVA), polyacrylics or copolymers thereof, polyphenols such as tannic acid, epigallocatechin gallate, epicatechin gallate, epigallocatechin, raspberry ellagitannin, theaflavin-3-gallate, tellimagrandin II, and the like. Advantageous coupling layers can be formed on the surface of the substrate by solution coating, by applying the coupling layer as a melt, or by bonding the coupling layer in the form of a film onto the substrate via methods such as ultrasonic welding, hot plate welding, vibration welding, solvent bonding, UV bonding, roll bonding, and adhesive bonding. The coupling layer can have a thickness of less than about 1 mm, such as less than 100 pm or less than about 50 pm or less than 10 pm and even less than 1 pm, such as less than 500 nm, or between and including such values.

[0020] Reactive components useful in the formulations of the present disclosure include reactive components having one end that can be attached to the substrate surface, for example, covalently bonded to a reactive group on the surface to form an assembly of compounds. Such reactive components preferably have a chain length of at least three carbons. Other useful reactive components include polymerizable monomers that can react to form an array of linear polymers with an end fixed to the surface and the other end extending away from the surface. To increase the rate at which the coating is formed, the reactive components of the formulation are selected to undergo a condensation reaction with the loss of small molecules such as water, alcohol, etc., which can be easily removed to drive the reaction to near completion under ambient temperature and pressure. The linear polymers, preferably having one end attached to the surface and the other end extending away from the surface, do not form covalent bonds or crosslinks with adjacent linear polymers (e.g., form brush-like structures). The lack of crosslinks allows for greater mobility of the chains and ends extending away from the surface in the deposited lubricant of the repellent coating system.

[0021] Reactive components useful in the formulations of the present disclosure include, for example, low molecular weight silanes or siloxanes having one or more hydrolyzable groups. Such silanes or siloxanes have a molecular weight of less than about 1,500 g / mol, such as less than about 1,000 g / mol, and include monoalkyl or mono-fluoroalkyl phosphonic acids, such as 1H,1H,2H,2H-perfluorooctane phosphonic acid, alkoxysilanes, such as mono-alkoxysilanes, such as alkyl, fluoroalkyl and perfluoroalkyl mono-alkoxysilanes, trimethylmethoxysilane, dialkoxysilanes, such as dialkyldialkoxysilanes, such as C 1~8Dialkyldialkoxysilanes, such as dimethyldimethoxysilane, dimethoxy(methyl)octylsilane, dialkoxy, diphenylsilane, diethyldiethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diisobutyldiethoxysilane, isobutylisopropyldimethoxysilane, dicyclopentyldimethoxysilane, dialkoxy, fluoroalkyl or perfluorosilanes, dimethoxy-methyl(3,3,3-trifluoropropyl)silane, (3,3,3-trifluoropropyl)silane, perfluoroalkyl-trialkoxysilanes, trimethoxy(3,3,3-trifluoropropyl)methyldimethoxysilane, alkyltrimethoxysilanes, trialkoxysilanes, such as perfluoroalkyl-trialkoxysilanes, trimethoxy(3,3,3-trifluoropropyl)silane, trimethoxymethylsilane, 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, 1H,1H,2H,2H-perfluorodecyltriethoxysilane, nonafluorohexyltrimethoxysilane, nonafluorohexyltriethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl)trimethoxysilane, silane, tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane, heptadecafluoro-1,1,2,2-tetrahydrodecyl)trimethoxysilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl)triethoxysilane, chlorosilanes such as octyldimethylchlorosilane, dichlorosilanes such as diethyldichlorosilane, di-n-butyldichlorosilane, diisopropyldichlorosilane, dicyclopentyldichlorosilane, di-n-hexyldichlorosilane, dicyclohexyldichlorosilane, di-n -Octyldichlorosilane, 3,3,3-trifluoropropyl)methyldichlorosilane, nonafluorohexylmethyldichlorosilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl)methyldichlorosilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl)methyldichlorosilane, (3,3,3-trifluoropropyl)dimethylchlorosilane, nonafluorohexyldimethylchlorosilane, tridecafluoro-1,1,2,2-tetrahydrooctyl)dimethylchlorosilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl)dimethylchlorosilane, trichlorosilanes such as (tridecafluoro-1,1,2,2-tetrahydrooctyl)trichlorosilane, (3,3,3-trifluoropropyl)trichlorosilane, nonafluorohexyltrichlorosilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl)trichlorosilane, aminosilanes such as nonafluorohexyltris(dimethylamino)silane, etc.

[0022] The alkoxy groups of such reactive moieties are 1~4 Alkoxy groups, such as methoxy (-OCH3) , ethoxy (-OCH2CH3) The alkyl group of such a reactive component may be, for example, a C 3~30 C etc. 1~30 The alkyl groups of such reactive components that form linear polymers can have a variety of chain lengths, such as, for example, C 1~8 C etc. 1~16 The alkyl group in each case generally has a lower alkyl group of C 1~30 , C 3~30 , C 1~16 , C 1~8 and the like, for example, fluoroalkyl or perfluoroalkyl groups forming fluoroalkyl or perfluoroalkyl alkoxysilanes, difluoroalkyl or diperfluoroalkyl dialkoxysilanes, fluoroalkyl or perfluoroalkyl trialkoxysilanes having such chain lengths.

[0023] The tie layer can be formed from the formulation by reacting the reactive components of the formulation directly with the exposed hydroxyl or other reactive groups on the surface of the substrate to form an array of linear compounds with one end covalently bonded directly to the surface via the hydroxyl or other reactive groups on the surface of the substrate. Alternatively, the tie layer can be formed by polymerizing one or more silane monomers directly from the exposed hydroxyl or other reactive groups on the surface of the substrate to form an array of linear polysilanes or polysiloxanes or combinations thereof covalently bonded directly to the surface via the hydroxyl or other reactive groups on the surface of the substrate. Preferably, the linear polymers having one end bonded to the surface and the other end extending away from the surface do not form covalent bonds or crosslinks with adjacent linear polymers (e.g., form brush-like structures).

[0024] The tie layer can have a thickness of less than about 1000 nm. In some cases, the thickness of the tie layer can be less than about 500 nm, less than about 100 nm, or even less than about 10 nm, for example, from about 1 or 5 nm to about 500 nm.

[0025] One or more catalysts can be included in the formulation of the present disclosure. In this specification, catalyst refers to one or more catalysts. Catalyst can facilitate and promote the formation of bonding layer. Useful catalysts that can be included in the formulation include acid catalysts, such as sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid, or combinations thereof. In some embodiments, catalyst does not include catalysts that include transition metals such as platinum, because such catalysts increase cost and tend to remain in the formed coating that includes such catalysts.

[0026] The formulations of the present disclosure also include a solvent or medium, which may be a single solvent or multiple solvents, such as a solvent system, collectively referred to herein as a solvent. The solvent may facilitate the formation of a bonding layer and the infusion of a lubricant into the bonding layer during the formation of a repellent coating on the surface. Preferably, the solvent should have a relatively low boiling point and a relatively high vapor pressure to facilitate the evaporation of the solvent from the formulation during the formation of the repellent coating from the formulation. In an embodiment, the solvent of the formulations of the present disclosure may have a boiling point of about 140° C. or less at atmospheric pressure, such as about 82.5° C. or less and even about 60° C. or less. In other embodiments, the solvent of the formulations of the present disclosure may have a vapor pressure of 4.3 kPa at 20° C., such as isopropyl alcohol. Solvents with higher boiling points and lower vapor pressures may be used, but may tend to inhibit the drying rate and / or may need to be removed by application of a reduced pressure atmosphere to remove the solvent.

[0027] Useful solvents that can be included in the formulations of the present disclosure include one or more lower ketones, such as C ketones, such as acetone, methyl ethyl ketone, cyclohexanone, etc. 1~8 Ketones, lower alcohols such as methanol, ethanol, isopropanol, butanol, etc. 1~8 Alcohols, lower ethers, such as dimethyl ether, diethyl ether, and tetrahydrofuran, 1~8 Ethers, lower esters, such as ethyl acetate, butyl acetate, glycol ether esters, etc. 1~8 Esters, lower halogenated solvents such as methylene chloride, chloroform, etc. 1~8 The solvent may include an aliphatic or aromatic hydrocarbon solvent, such as hexane, cyclohexane, toluene, xylene, dimethylformamide, dimethylsulfoxide, and any combination thereof. The solvent may also include an amount of water, for example, less than about 5% by weight water.

[0028] The formulations of the present disclosure also include a lubricant or combination of lubricants, which are collectively referred to herein as lubricants. To form a lubricant stably attached to the bonding layer formed from the reactive components of the formulation, the lubricant should have a strong affinity for the bonding layer and / or substrate so that the lubricant can completely wet the surface (e.g., the equilibrium contact angle is less than about 5°, e.g., less than about 3°, less than 2°, less than 1°) and stably attach to the surface. Furthermore, since it is intended that the solvent will be removed from the formulation and the lubricant will attach to the bonding layer when forming the repellent coating, the lubricant should have a boiling point significantly higher than that of the solvent, e.g., the boiling point of the lubricant should be at least 10° C. higher than the solvent at the same atmospheric pressure, e.g., at least 20° C., 40° C., 60° C., 80° C., 100° C., 120° C., 150° C., 200° C., 250° C., etc. higher than the solvent at the same atmospheric pressure. Moreover, the lubricant should be mobile in the formed repellent coating, and therefore it is preferred that the lubricant does not substantially react, if at all, with the reactive components in the formulation. It is believed that the lubricant stably adheres to the bonding layer mainly through van der Waals forces, rather than through covalent bonding to the bonding layer. In certain embodiments, the lubricant of the present disclosure does not have groups that would react with the reactive components of the formulation.

[0029] Furthermore, a stably adherent lubricant is distinguished from a lubricant disposed on a surface or modified surface that does not wet the surface (e.g., forms an equilibrium contact angle of greater than 10°) and / or simply slides off the surface within minutes or less once the surface is raised to a sliding angle of 90°. A stably adherent lubricant to a bonding layer is one that remains substantially (greater than about 80%) on the bonding layer for at least an hour, or for longer periods such as hours, days, and months, even when the surface substrate is at 90° from horizontal.

[0030] Lubricants useful in the formulations of the present disclosure should be relatively mobile while having sufficient viscosity to facilitate repellency of the coating system at temperatures intended for use with substrates having repellent coatings. Such temperatures may range from about -30°C to about 300°C. Thus, the lubricant should preferably have a viscosity of at least about 1 cSt (measured at 25°C), such as at least about 2 cSt, 3 cSt, 4 cSt, 5 cSt, 6 cSt, 7 cSt, 8 cSt, 9 cSt, 10 cSt, 15 cSt, 20 cSt, 30 cSt, etc. (measured at 25°C), and any value therebetween. Furthermore, the lubricant should preferably have a viscosity of about 1500 cSt or less measured at 25°C, such as about 950 cSt or less, about 900 cSt or less, about 850 cSt or less, etc., measured at 25°C, and any value therebetween, so that the lubricant may be mobile at certain temperatures where the repellent coating may be used. In one embodiment, the lubricant for the formulation of the present disclosure can have a viscosity ranging from about 1 cSt to about 1500 cSt, for example, from about 2 cSt, 3 cSt, 4 cSt, 5 cSt, 6 cSt, 7 cSt, 8 cSt, 9 cSt, 10 cSt, 15 cSt, 20 cSt, 30 cSt, etc., measured at 25°C, to about 1500 cSt, 1200 cSt, 1000 cSt, 800 cSt, 350 cSt, 200 cSt, 150 cSt, etc., and any value therebetween. For high temperature applications, the repellent coating may have a lubricant with an even higher viscosity at room temperature, since the viscosity of such a lubricant becomes lower at higher operating temperatures. Additionally, the viscosity of the lubricant may be less than about 2 g / cm. 3 A lubricant density of less than 0.1 would be preferred in the temperature range of 15°C to 25°C.

[0031] The lubricant included in the formulation of the present disclosure may be one or more of omniphobic lubricants, hydrophobic lubricants and / or hydrophilic lubricants. The lubricant may include perfluorinated oils or silicone oils or hydroxypolydimethylsiloxanes (PDMS) or vegetable oils. Other lubricants that may be used include perfluoropolyethers, perfluoroalkylamines, perfluoroalkyl sulfides, perfluoroalkyl sulfoxides, perfluoroalkyl ethers, perfluorocycloether oils and perfluoroalkyl phosphines and perfluoroalkyl phosphine oxide oils and mixtures thereof. Preferably, the lubricant is selected to have a strong chemical affinity for a particular bonding layer and / or substrate so that the lubricant can thoroughly wet and stably adhere to the surface through the bonding layer. For example, perfluorinated oils such as perfluoropolyethers (e.g., Krytox oil) can thoroughly wet and stably adhere to polymeric siloxanes and / or silane bonding layers that include fluorinated alkylsilanes such as perfluorinated alkylsilanes. Such a bonding layer can be formed from reactive fluoroalkylsilanes in the formulation that react with functional groups on the surface of the substrate. Silicone oils or vegetable oils can fully wet and stably attach to a bonding layer composed of, for example, an array of linear polydimethylsiloxane (PDMS). Hydroxy PDMS can also fully wet and stably attach to a bonding layer composed of, for example, an array of linear polydimethylsiloxane (PDMS). Such a PDMS bonding layer can be formed from polymerizing dimethyldimethoxysilane from the surface of the substrate. Mineral oils or vegetable oils can fully wet and stably attach to a bonding layer comprising an array of alkylsilanes, which can be formed from alkyltrichlorosilanes or alkyltrimethoxysilanes. The alkyl groups on such alkylsilanes can be of various chain lengths, for example C 1~30Other lubricants that may be compatible with polysiloxanes polymerized from alkyl silanes of various chain lengths and one or more dialkyldialkoxysilanes, such as dimethyldimethoxysilane, include alkane oils, as well as vegetable oils, such as vegetable oil, avocado oil, algae extract oil, olive oil, palm oil, soybean oil, canola oil, castor oil, rapeseed oil, corn oil, peanut oil, coconut oil, cottonseed oil, palm oil, safflower oil, sesame oil, sunflower seed oil, almond oil, cashew oil, hazelnut oil, macadamia oil, mongongo nut oil, pecan oil, pine nut oil, groundnut oil, walnut oil, grapefruit seed oil, lemon oil, orange oil, amaranth oil, apple seed oil, argan oil, avocado oil, babassu oil, ben oil, borneo tallow nut oil, cape chestnut oil, and the like. oil, carob pod oil, camellia seed oil, cocoa butter, cocklebur oil, cohune palm oil, grape seed oil, kapok seed oil, kenaf seed oil, Lallemantia oil, Manila oil, meadowfoam seed oil, macadamia nut oil, mustard oil, okra seed oil, papaya seed oil, Pequi oil, poppy seed oil, pracaxi oil, prune kernel oil, quinoa oil, ramtil oil, rice bran oil, rapeseed oil, sesame oil, safflower oil, sapote oil, shea butter, squalene, soybean oil, tea seed oil, tigernut oil, tomato seed oil, liquid terpenes (e.g., Citropol®) and other similar plant-based oils. The vegetable-based oils may be used alone or with other lubricants, or as mixtures of vegetable-based oils alone or with other lubricants.

[0032] Other ingredients can be included in the formulations of the present disclosure, such as fragrances, i.e., substances that produce a pleasant odor. Such fragrances include, for example, natural or synthetic aromatic compounds or essential oils, such as lemon oil, bergamot oil, lemongrass oil, orange oil, coconut oil, peppermint oil, pine oil, rose oil, lavender oil, or any combination of the above. As an example, the fragrance added to the formulations of the present disclosure can have an odor of lemon or rose or lavender or coconut or orange or apple or wood or peppermint. One or more fragrances can be added to the formulations of the present disclosure as is, for example, without dilution and in place of a solvent, in the range of about 0.0005 parts by weight to about 10 parts by weight, for example, about 0.01 to about 5 parts by weight. In certain embodiments, the fragrance is soluble in alcohol and siloxane.

[0033] In certain embodiments, the concentrations of the various components on a weight basis in the formulations of the present disclosure may include the ranges presented in the table below.

[0034] [Table 1]

[0035] [Table 2]

[0036] [Table 3]

[0037] For some embodiments of the formulations of the present disclosure, the lubricant concentration is about 50% by weight or less, for example, about 0.05% by weight to about 50% by weight. Lubricant concentrations greater than 99% by weight tend to inhibit the formation of a repellent coating system on the surface.

[0038] In an embodiment of the present disclosure, a repellent coating system can be formed on a substrate from fluorinated alkylsilanes and / or fluorinated lubricants. For example, one or more C2-C8 fluorinated alkylsilane reactive components (e.g., about 2% to about 10% by weight) can be combined in an all-in-one formulation with one or more perfluoropolyether lubricants (e.g., about 0.02% to about 10% by weight), a catalyst, and a solvent. Such a formulation can be applied, for example, onto a glass substrate.

[0039] Advantageously, the formulations of the present disclosure can have a long shelf life without substantial deactivation of the reactive components when stored in a closed container at about room conditions, and can then be readily used to prepare repellent coatings.

[0040] Repellent coatings prepared from the formulations of the present disclosure are capable of repelling a wide range of liquids and solids, including but not limited to rain water, soapy water, hard water, blood, bacteria, etc., with a typical contact angle hysteresis of less than about 10°. Repellent coatings also have a typical contact angle hysteresis of at least 1×10 -3 It is also possible to repel viscoelastic solids having a dynamic viscosity of at least 1 Pa·s, e.g., at least 1 Pa·s, 100 Pa·s, 10,000 Pa·s to 100,000 Pa·s.

[0041] In carrying out certain aspects of the present disclosure, it is preferred to form a repellent coating on a substrate having a relatively smooth surface.In some embodiments, the substrate surface has an average roughness (Ra) at a microscale level, for example less than a few microns, and preferably less than a few hundreds of nanometers, or even less than a few nanometers.Advantageously, the surface of the substrate on which the repellent coating is formed is relatively smooth, for example, the surface has an average roughness Ra of less than about 4 pm, for example less than about 2 pm and less than about 1 pm, and even less than about 500 nm, for example less than about 100 nm, less than 80 nm, less than 60 nm, less than 40 nm, less than 20 nm, less than 10 nm, etc.

[0042] The average surface roughness is 2 x 2 pm over the scanning area. 2 The average surface roughness can be measured by an atomic force microscope (AFM) using a tapping mode of 0.1 nm to measure the average surface roughness at 0.1 nm scale, or by an equivalent technique. The average surface roughness can be measured on an area of ​​475 × 475 nm to measure the average surface roughness at 1 nm scale. 2 The surface roughness can be measured by a Zygo optical profilometer from , or by equivalent techniques.

[0043] In carrying out certain aspects of the present disclosure, substrates having a smooth surface that may be used in the present disclosure include those composed of one or more polymers, such as polycarbonate, polypropylene, high density polyethylene, polyurethane, poly(methyl methacrylate), silicone, nylon, poly(ethylene-vinyl acetate), polyvinyl acetate, polyvinyl alcohol, building / construction materials, such as marble, granite, stone, terracotta, brick, asphalt, cement, ceramic, china, porcelain, glass, metals, such as titanium, copper, aluminum, carbon steel, metal alloys, cellulose, such as wood, paper, cotton, other materials found in the solid state, and combinations thereof. The surface of the substrate can be treated, for example, by oxygen plasma treatment, or by heating in the presence of air or oxygen (in the case of metals), to form reactive groups, such as hydroxyl groups. The substrate can include a reactive coupling layer and a repellent coating formed on the surface of the coupling layer.

[0044] The substrate surface can be cleaned and dried prior to application of the formulation. One example of cleaning the substrate surface includes using a lower alcohol, such as ethanol or isopropanol, to rinse the surface. The surface can then be dried and the formulation applied.

[0045] The method of preparing a repellent coating on the surface of a substrate includes drying the formulation of the present disclosure on the surface of the substrate to substantially remove the solvent, for example, more than about 60%, 65%, 70%, 80%, 85%, 90%, 95% and more by weight of the solvent can be removed in the drying step. Drying the formulation concentrates the reactive components, which react to form a bonding layer on the surface of the substrate. The reactive components are selected to react with the surface to form an array of compounds having one end bonded to the surface and the other end extending away from the surface. Drying the formulation also concentrates the lubricant and retains it in the bonding layer. Thus, the lubricant is selected to have an affinity for the bonding layer and / or the surface, so that it can stably adhere to the surface via the bonding layer.

[0046] The repellent coating on the surface of the substrate can be advantageously formed by drying at a relatively low temperature, for example, at a temperature ranging from about 0°C to about 80°C. Thus, the formation of the repellent coating from the formulation of the present disclosure can be carried out at a temperature between about 5°C to about room temperature, for example, 20°C, and at elevated temperatures, for example, above about 25°C, 30°C, 40°C, 50°C, 55°C, 60°C, 70°C, 80°C, and the like. The formation of the repellent coating can advantageously be carried out in a relatively short time, for example, in a time period of about 120 minutes or less, such as 60 minutes, for example, in a short time period of about 30 minutes or less, and even about 5 minutes or less. Although a vacuum can facilitate drying of the formulation, it is not essential to the method, and the drying of the formulation of the present disclosure can be carried out at atmospheric pressure, for example, about 1 atm. Furthermore, the drying and / or application of the formulation of the present disclosure can be carried out in air or in an inert atmosphere, for example, a nitrogen atmosphere.

[0047] The application of the formulation of the present disclosure to the surface of the substrate can be carried out in a liquid phase process, thereby avoiding complex equipment and processing conditions. Such liquid phase processes include applying the formulation to the substrate surface, for example, by simply immersing the substrate (dip coating), or by wiping, spraying (including aerosol spray), curtain coating and / or spin coating the formulation onto the surface. Another method of applying the formulation of the present disclosure to the surface of the substrate can be carried out by wiping a towel made of fabric, paper or similar material, or a sponge or squeegee, infused with the formulation, onto the surface and transferring the formulation from the towel, sponge, squeegee to the surface of the substrate. Advantageously, the formulation can be applied to the substrate surface at ambient temperature and / or atmospheric pressure as well as in air, for example, the formulation of the present disclosure can be applied to the substrate surface in air and at atmospheric pressure. In certain embodiments, the formation of the bond layer is promoted in the presence of a catalyst, for example an acid catalyst, and water. The water can be available from a solvent or from the atmosphere or both. Drying the formulation in an atmosphere having some moisture, for example at least about 10% ambient humidity at 20° C. and atmospheric pressure, is preferred for certain reactive components. Thus, in some embodiments, the formulations of the present disclosure are dried at about 10% to about 80% ambient humidity or less.

[0048] Forming a repellent coating by applying and drying the formulation of the present disclosure can advantageously be carried out in a relatively short time, for example, in a time of about 120 minutes or less, such as 60 minutes, for example, about 30 minutes or less, and even about 5 minutes or less. Furthermore, drying and / or applying the formulation of the present disclosure can be carried out in air or in an inert atmosphere, such as a nitrogen atmosphere, and at atmospheric pressure. Advantageously, the repellent coating can be formed on the substrate surface under ambient conditions (for example, in air under about 1 atmosphere, and at a temperature of about 5°C to about 35°C).

[0049] FIG. 1 illustrates a method of forming a repellent coating on a surface of a substrate according to one embodiment of the present disclosure. In this example, a formulation (10) of the present disclosure is applied to a substrate (12) to form a substrate (14) having a formulation coating thereon. In this example, the substrate is a smooth substrate (e.g., a substrate having a surface with an average roughness of less than 1 pm). Upon drying the formulation on the surface of the substrate to substantially remove the solvent, a tie layer (16a) is covalently bonded to the surface (12a) and a lubricant layer (16b) is infused into the tie layer (16a) to form a repellent coating (16). The tie layer resembles a brush on the surface of the substrate, with the lubricant infused within the tie layer.

[0050] FIG. 2 illustrates another method of forming a repellent coating on a surface of a substrate according to one embodiment of the present disclosure. In this example, a coupling layer (28) is first applied to the surface (22a) of a substrate (22). The coupling layer is useful for substrates with relatively inert surfaces, such as many surfaces composed of polymeric components. A formulation (20) of the present disclosure is applied to the surface (28a) of the coupling layer (28) to form a substrate (24) having a formulation coating thereon. Upon drying the formulation on the surface to substantially remove the solvent, a bonding layer (26a) is covalently bonded to the surface (28a) and a lubricant layer (26b) is infused into the bonding layer (26a) to form a repellent coating (26). The bonding layer resembles a brush on the surface of the substrate, with the lubricant infused within the bonding layer.

[0051] In some instances and under certain conditions, the lubricant of the repellent coating may become depleted over time. Advantageously, the lubricant can be replenished by applying a lubricant, either the same or a different lubricant than that used to prepare the repellent coating, to the bonding layer to refresh the repellent coating system on the surface of the substrate.

[0052] Exemplary formulations of the present disclosure may include one or more polymerizable silane and / or siloxane monomers as reactive components. When such formulations are dried, the monomers polymerize from the hydroxyl groups exposed on the surface, forming an array of linear polysilanes or polysiloxanes or combinations thereof. This technique produces an array of linear polymers with one end covalently bonded to the surface and the other end extending away from the surface, resembling a brush. Exemplary formulations with ranges for polymerizable monomers, lubricants, solvents and acid catalysts are presented in Tables 1 and 2 below, and in Table 3 below, along with fragrances.

[0053] [Table 4]

[0054] [Table 5]

[0055] [Table 6]

[0056] A particular exemplary formulation includes dimethyldimethoxysilane as the polymerizable silane monomer and can comprise about 4% to about 15% by weight of the formulation, for example about 4.5% to about 9.0% by weight, and the lubricant is a silicone oil or a hydroxyl-terminated polydimethylsiloxane or a vegetable oil (e.g., soybean oil) and can comprise about 0.05 to about 50% by weight of the formulation. The viscosity of the silicone oil or the hydroxyl-terminated polydimethylsiloxane or the vegetable oil can range from about 20 cSt to about 350 cSt at 25° C. In this particular example, the solvent can be a lower ketone or alcohol, such as acetone, ethanol, isopropanol (or isopropyl alcohol), a lower chlorinated solvent, such as chloroform, and the like, and any combination of the foregoing, and can comprise about 45.0% to about 95.0% by weight of the formulation. In this particular example, sulfuric acid and / or hydrochloric acid or acetic acid or phosphoric acid can be used as a catalyst and can comprise about 0.5% to about 1.0% by weight of the formulation.

[0057] To demonstrate the effectiveness of certain formulations of the present disclosure, a smooth glass slide was cleaned with isopropanol, followed by application of the formulation by wiping onto the slide. The slide was then left for 5 minutes under ambient conditions of 23° C., 60% relative humidity, and atmospheric pressure. After drying, repellent coatings were formed on the surface of the glass slide using the formulations with various concentrations of components. All repellent coatings tested showed low sliding angles (less than 10°) for a 20 μL water droplet. It should be noted that a smaller sliding angle represents better liquid repellency of the coated surface against a particular liquid. Furthermore, the lubricant was stable on the surface and did not dewet. The resulting coatings were capable of repelling a wide range of liquids and solids, including but not limited to rainwater, soapy water, hard water, and blood, with a typical contact angle hysteresis of less than 10°. The repellent coatings also showed a contact angle of at least 1×10 -3 It can repel viscoelastic solids with dynamic viscosities of Pa·s, 1 Pa·s, 100 Pa·s, 10,000 Pa·s to 100,000 Pa·s.

[0058] Advantageously, the formulations of the present disclosure may be applied to surfaces such as ceramic or metallic toilets, sinks, sanitary ware surfaces, mirrors, windshields, building windows, surfaces of glass substrates including glass optical lenses for cameras, surfaces composed of one or more polymers such as plastic sinks, toilets, personal protective equipment such as gowns, face shield goggles, shoe covers and shoes, and medical devices such as stoma appliances, catheters, syringes, scalpels, endoscope lenses, metal and plastic implants (e.g. orthopedic implants, dental implants, glaucoma implants), prosthetic devices, windshields, camera lenses, lamps and sensing casings, mudguards, automotive parts such as car bodies, windshields, aircraft parts such as aircraft wings and bodies, underwater equipment, cables, nautical parts such as ships and boats, outdoor and indoor signage, bus station enclosures.

[0059] Many medical devices, including those that are composed of polymer surfaces, can benefit from the formulations and repellent coatings of the present disclosure. For example, stoma appliances (commonly referred to as bags or pouches) can include one or more ports, including collection pouches and one or more exit ports. Such stoma appliances typically have a surface that is made of one or more polymers that can be coated with the formulations of the present disclosure to form one or more repellent surfaces. In one aspect of the present disclosure, the surface, e.g., the inner surface, of a stoma appliance can include a repellent coating by drying the formulations of the present disclosure on such a surface to substantially remove the solvent and form a bonding layer on the surface with the lubricant stably attached to the bonding layer.

[0060] Moreover, surfaces composed of certain polymeric components that tend to be relatively inert and resistant to modification can also benefit from the formulations and repellent coatings of the present disclosure. For such surfaces, a coupling layer can be applied to the polymeric substrate and the repellent coating system of the present disclosure can be prepared on the surface of the coupling layer. EXAMPLES

[0061] The following examples are intended to further illustrate certain preferred embodiments of the invention, but are not limiting in nature. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, numerous equivalents to the specific substances and procedures described herein.

[0062] The following example formulations (Example 1-Example 5) vary in the concentration of lubricant in the formulation while keeping the other ingredients constant with respect to each other, i.e., the approximate weight ratio of solvent (wt%):silane monomer (wt%):catalyst (wt%)=100:10:1. For the formulations of Examples 1-5 below, the formulations were prepared by mixing the ingredients in a container for about 1 minute by stirring with either a vortex mixer or a magnetic stirrer. The formulations were allowed to stand at room temperature for about 2 minutes before use. The formulations are stable for at least 3 months after preparation.

[0063] For these experiments, smooth glass slides were used as substrates. The surface roughness of the glass slides was less than about 10 nm. The glass slides were cleaned by rinsing with isopropanol before application of the formulations. The formulations having the ingredients and concentrations of Examples 1-5 were applied to different glass slides by dip coating or spraying, followed by wiping the formulations onto the glass slides.

[0064] [Table 7]

[0065] [Table 8]

[0066] [Table 9]

[0067] [Table 10]

[0068] [Table 11]

[0069] After the formulation was applied to the glass slide, the formulation was then dried under ambient conditions (e.g., 23 °C, 60% relative humidity, atmospheric pressure) for 5 min to form a repellent surface on the glass slide. Subjecting the formulation to these drying conditions resulted in the dimethyldimethoxysilane monomers polymerizing by an acid-catalyzed condensation method to form an array of linear polysiloxanes attached to the glass surface, with the silicone oil stably immobilized within the polysiloxane polymer. The estimated thickness of the grafted PDMS layer on the glass is approximately 1-4 nm according to X-ray photoelectron spectroscopy (XPS) analysis.

[0070] All of the formulations in Examples 1-5 produced repellent surfaces that exhibited low sliding angles (less than 10°) for a 20 μL water droplet. To measure the sliding angle, a water droplet of known volume (e.g., 20 pL) is placed on the coated substrate. The substrate is then gradually tilted from a horizontal position until the water droplet begins to slide off the substrate. The angle at which the water droplet begins to slide (formed between the horizontal and the smooth tilted substrate) is the sliding angle. Additionally, the lubricant was stable on the surface and did not dewet.

[0071] The shelf life of certain example formulations above was determined to be stable for over 12 months. For example, certain formulations were prepared and tested by coating glass 12 months after preparation, and the repellent coating was found to provide a sliding angle of 10 degrees or less, similar to the results when the formulations were prepared.

[0072] The sliding angle was measured by a tilt stage or a goniometer.

[0073] FIG. 3 is a graph showing slide angle versus lubricant concentration for repellent surfaces prepared from formulations including those from Examples 1-5 above.

[0074] As can be seen from the data in Figure 3, when the lubricant concentration is within the range of about 0.1 wt% to about 10 wt%, the sliding angle of a 20 pL droplet is less than 10 degrees. Note that the weight ratio of the other components is constant, that is, solvent (wt%): reactive monomer (wt%): catalyst (wt%) = 100:10:1.

[0075] FIG. 4 shows a plot of the sliding angle as a function of the mass ratio between the lubricant and the reactive component prepared from an all-in-one formulation containing a reactive component, a catalyst, a solvent, and a lubricant. In the plot data, the reactive monomer, the solvent, the catalyst, and the lubricant were dimethyldimethoxysilane, isopropanol, sulfuric acid, and silicone oil, respectively. From the formulation data, the mass ratio ( m 潤滑剤 / m 反応性成分) It was observed that the sliding angle of a 20 pL water droplet was smaller than 10 degrees when the pH was in the range of about 0.01 to about 1. Note that the weight ratio of the other components was constant, solvent (wt%): reactive component (wt%): catalyst (wt%) = 100:10:1. Error bars represent the standard deviation of five independent measurements.

[0076] These examples demonstrate that repellent coatings on the surface of substrates can be advantageously formed from single formulations by single application therefrom under ambient conditions (i.e., in air at atmospheric pressure and temperature) and by liquid phase processing, thereby avoiding complex equipment and processing conditions.

[0077] In real world applications, the all-in-one formulations containing fragrance were applied to toilets, sinks, fixtures, and glass including mirrors or windshields, building windows, solar panels, brass handrails and medical equipment such as optical lenses for cameras and stoma appliances and personal protective equipment such as crocs safety shoes. The coatings were applied to these surfaces by spray coating or wiping. The following formulations were coated on the following substrate surfaces:

[0078] [Table 12]

[0079] [Table 13]

[0080] [Table 14]

[0081] Formulations having the ingredients and concentrations of Examples 6, 7, and 8 were applied to a ceramic toilet, a ceramic sink, and a glass mirror, respectively. Prior to application of the formulations, the uncoated surfaces were cleaned by wiping with isopropanol or glass cleaner, then dried. The formulations were applied to clean, dry surfaces by spraying the formulations, followed by wiping, or by wiping the formulations directly onto the surface with a paper towel, cloth, sponge, or any other similar fabric. Any undesirable residual haze on the surface was removed by wiping or rinsing with isopropanol or glass cleaner, followed by wiping with a paper towel, cloth, sponge, or any other similar fabric.

[0082] After application of the formulations, the toilet, sink and mirror were allowed to dry for about 5 minutes under ambient conditions (e.g., about 23° C., 60% relative humidity, atmospheric pressure). After drying, the formulations of Examples 6, 7 and 8 were used to form repellent coatings on the surfaces of the toilet, sink and mirror, respectively. All of the coated surfaces were capable of repelling water droplets of more than 15 μL. Furthermore, the lubricant was stable on the surface and did not dewet. The resulting coatings were capable of repelling a wide range of liquids and solids.

[0083] [Example 9] Polymer Surface Substrates with relatively unreactive surfaces can also benefit from the formulations and repellent coatings of the present disclosure.In these examples, reactive coupling layers are applied to the substrate surface before applying the formulation.Reactive coupling layers, including silica coupling layer, poly(ethylene-vinyl acetate) coupling layer and poly(vinyl alcohol) coupling layer, are applied to polymer substrates.

[0084] For example, a nylon substrate was first treated with a silica coupling layer. The silica layer was formed on the nylon sheet by a sol-gel method. Specifically, the nylon sheet was dip-coated or wipe-coated with a solution containing TEOS (tetraethyl orthosilicate) / ethanol / H2O / HCl (volume ratio 1:4:6:0.1). Following dip-coating, the nylon substrate was cured at room temperature for 12 hours. To increase the thickness of the silica layer, multiple silica layers can be applied to each other by repeating this procedure.

[0085] In another example, a silica coupling layer was formed on the plastic surface of a stoma pouch (available from Hollister, Inc.) by dip-coating the stoma bag with a solution containing TEOS (tetraethyl orthosilicate) / ethanol / HO / HCl (volume ratio 1:4:6:0.1).

[0086] In another example, a poly(ethylene-vinyl acetate) (PEVA) coupling layer was formed on a nylon sheet by melting and baking PEVA beads (sigma Aldrich, 40 wt % vinyl acetate) onto the nylon sheet in an oven at 120 °C for 1 h.

[0087] The formulations having the ingredients and concentrations of Example 2 above were then applied to the polymer substrate surfaces having various coupling layers by dip coating or spraying or wiping the formulation onto the surface. All of the coated polymer surfaces formed repellent surfaces that exhibited low sliding angles (less than 25°) for a 15 μL water droplet (Table 4).

[0088] The above coating method is also applicable to polyurethane, polycarbonate, polypropylene, high density polyethylene, polyvinyl chloride, EVA film, poly(methyl methacrylate), and silicone (see Table 4).

[0089] [Table 15]

[0090] In a simulated restroom environment, our coating was more effective at preventing mineral scaling on glass than uncoated glass surfaces. Specifically, hard water droplets (200 mg / L sodium chloride) can move about an order of magnitude faster on repellent coated surfaces than on uncoated surfaces under the intended test conditions, and evaporate about 1.5 times slower on repellent coated surfaces than on uncoated surfaces. Faster moving, slower evaporating hard water droplets are more likely to be removed before leaving behind mineral residue, which should make the repellent coated surfaces more effective at preventing scaling. After 100 hard water rinse cycles, the repellent coated surfaces showed over 95% reduction in hard water buildup in terms of areal coverage than untreated glass.

[0091] Accelerated UV exposure testing was performed at 3600 MJ / m at wavelengths from 280 to 400 nm at a nominal relative humidity of 31% and a temperature of 22°C. 2 The test was performed at a cumulative dosage of 1000 x 1000 / year. Contact angle, sliding angle and contact angle hysteresis tests were performed on the repellent coated glass samples before and after UV accelerated testing. Contact angle measurements were greater than 100°, contact angle hysteresis less than 10°, sliding angle less than 10°, and light transmission greater than 90% to 95% from 350 nm to 1500 nm. These results suggested that the repellent coated glass samples maintained similar liquid repellency even after the equivalent of 30 months of sunlight exposure. Measurements were performed using an Optronic Laboratories Monochromator Model OL750-D, S / N 14516191 (Solar Light Company Inc.).

[0092] To quantify the static lifetime of repellent coated glass samples made from the formulations provided in Example 2 (lubricant viscosities between 20 cSt and 350 cSt), the samples were stored at ambient conditions (average temperature and humidity of 23.5° C. and 40%, respectively) for 8 months and weighed periodically to determine lubricant loss due to evaporation. The sliding angle was measured and liquid repellency was quantified using a 15 μL water drop. The sliding angle of the samples remains below 10 degrees over the 8 months.

[0093] To evaluate the durability of the repellent coating under abrasive conditions, a 200 g weighted sandpaper was placed on the repellent coated glass sample with the abrasive side of the paper facing the sample. 100 grit aluminum oxide sandpaper was used. Each abrasive cycle consisted of pulling the sandpaper across the sample for 1 second at a speed of approximately 0.1 m / sec. After every few cycles, the sliding angle of a 15 pL water droplet was measured. The repellent coated sample (with the formulation of Example 2) withstood more than 700 aggressive abrasive cycles before the sliding angle of a 15 pL droplet reached more than 60 degrees.

[0094] [Table 16]

[0095] Only preferred embodiments of the invention and examples of its versatility are shown and described in this disclosure. It is to be understood that the invention is capable of use in various other combinations and environments and is susceptible to changes or modifications within the scope of the inventive concept expressed herein. Thus, for example, those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, numerous equivalents to the specific substances, procedures, and arrangements described herein. Such equivalents are considered to be within the scope of the invention and are encompassed by the following claims. The present invention includes the following embodiments. [Claim 1] A formulation comprising: (i) one or more reactive components capable of forming a bonding layer on a surface, said bonding layer comprising an array of compounds having one end bonded to the surface and another end extending away from the surface; (ii) an optional catalyst; (iii) a solvent; and (iv) a lubricant; the one or more reactive components are selected from the group consisting of alkoxysilanes, dialkoxysilanes, trialkoxysilanes, or combinations thereof; The lubricant has a viscosity of at least about 2 cSt when measured at 25° C. compound. [Claim 2] 2. The formulation of claim 1, wherein the relative amount by weight of the one or more reactive components to the lubricant in the formulation comprises 1 part reactive component to about 0.01 to about 1 part lubricant. [Claim 3] 2. The formulation of claim 1, wherein the formulation comprises the catalyst, the catalyst being an acid catalyst, and the catalyst being free of transition metals. [Claim 4] 4. The formulation of any one of claims 1, 2 or 3, wherein the one or more reactive components are one or more dialkyldialkoxysilanes. [Claim 5] 4. The formulation of claim 1, 2 or 3, wherein the lubricant is a silicone oil or a mineral oil or a vegetable oil or any combination thereof. [Claim 6] 4. The formulation of claim 1, 2 or 3, further comprising a fragrance. [Claim 7] A method for producing a repellent coating on a surface of a substrate from a formulation according to any one of claims 1, 2 or 3, comprising the steps of: drying the formulation on the surface of the substrate to substantially remove the solvent and form a tie layer on the surface with the lubricant stably adhered to the tie layer; the binding layer comprises an array of compounds having one end bound to a surface and another end extending away from the surface; method. [Claim 8] The method of claim 7 further comprising applying a lubricant to the bonding layer. [Claim 9] 8. The method of claim 7, wherein the formulation is dried in air and at atmospheric pressure. [Claim 10] 8. The method of claim 7, further comprising forming a coupling layer on the substrate and drying the formulation on a surface of the coupling layer. [Claim 11] 8. The method of claim 7, further comprising applying the formulation to the surface of the substrate in air and at atmospheric pressure. [Claim 12] The method of claim 7 , wherein the surface of the substrate is composed of glass, ceramic, or polymer. [Claim 13] 4. A method for producing a repellent coating on an ostomy appliance from a formulation according to any one of claims 1, 2 or 3, comprising the steps of: drying the formulation on the surface of the stoma appliance to substantially remove the solvent and form a tie layer on the surface with the lubricant stably adhering to the tie layer. method. [Claim 14] 14. The method according to claim 13, wherein the stoma appliance comprises a coupling layer, and the method comprises drying the formulation on a surface of the coupling layer. [Claim 15] A stoma appliance obtained according to claim 13 or 14. [Explanation of symbols]

[0096] 10 formulations 12 Base material 12a surface 14 Substrate having a compound coating on its surface 16 Repellent coating 16a bonding layer 16b Lubricants 20 Compounds 22 Base material 22a surface 24 Substrate having a compound coating on its surface 26 Repellent coating 26a bonding layer 26b Lubricants 28 Coupling Layer 28a surface

Claims

1. A formulation comprising: (i) one or more reactive components capable of forming a bonding layer on a surface, said bonding layer comprising an array of compounds having one end bonded to the surface and another end extending away from the surface; (ii) an acid catalyst; (iii) a solvent; and (iv) a lubricant; the one or more reactive components are selected from the group consisting of alkoxysilanes, dialkoxysilanes, trialkoxysilanes, or combinations thereof; The lubricant has a viscosity of at least 2 cSt when measured at 25° C. compound.

2. 10. The formulation of claim 1, wherein the relative amount by weight of the one or more reactive components to the lubricant in the formulation comprises 1 part reactive component to 0.005 to 10 parts lubricant.

3. 2. The formulation of claim 1, wherein the formulation comprises the catalyst, the catalyst being an acid catalyst, and the catalyst being transition metal-free.

4. 4. The formulation of any one of claims 1, 2 or 3, wherein the one or more reactive components are one or more dialkyldialkoxysilanes.

5. 4. The formulation of claim 1, 2 or 3, wherein the lubricant is a silicone oil or a mineral oil or a vegetable oil or any combination thereof.

6. The formulation of claim 1, 2 or 3, wherein the acid catalyst comprises sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, nitric acid, or a combination thereof.

7. A method for producing a repellent coating on a surface of a substrate from a formulation according to any one of claims 1, 2 or 3, comprising the steps of: drying the formulation on the surface of the substrate to substantially remove the solvent and form a tie layer on the surface with the lubricant stably adhered to the tie layer; the binding layer comprises an array of compounds having one end bound to a surface and another end extending away from the surface; method.

8. The method of claim 7 further comprising applying a lubricant to the bonding layer.

9. 8. The method of claim 7, wherein the formulation is dried in air and at atmospheric pressure.

10. The method of claim 7 further comprising forming a coupling layer on the substrate and drying the formulation on a surface of the coupling layer.

11. 8. The method of claim 7, further comprising applying the formulation to the surface of the substrate in air and at atmospheric pressure.

12. The method of claim 7 , wherein the surface of the substrate is composed of glass, ceramic, or polymer.

13. 4. A method for producing a repellent coating on an ostomy appliance from a formulation according to any one of claims 1, 2 or 3, comprising the steps of: drying the formulation on the surface of the stoma appliance to substantially remove the solvent and form a tie layer on the surface with the lubricant stably adhering to the tie layer. method.

14. The method according to claim 13, wherein the stoma appliance comprises a coupling layer, the method comprising drying the formulation on a surface of the coupling layer.

15. The method of claim 13 or 14, further comprising treating the surface with oxygen plasma prior to forming the bonding layer on the surface.

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