Fluorine-free hydrophobic permeable material

Abstract

The article comprises a permeable material having a surface; and a hydrophobic coating on the surface forming a hydrophobic surface, wherein the hydrophobic coating is fluorine-free, and the hydrophobic surface has a water contact angle of 95 degrees or greater. The article may be a vent. A method for producing a hydrophobic article comprises depositing a hydrophobic material onto a permeable material; and curing the hydrophobic material to form a hydrophobic surface. The hydrophobic coating may contain a siloxane.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims the benefits of U.S. Provisional Patent Application No. 63 / 456,327, filed on 31 March 2023, and U.S. Provisional Patent Application No. 63 / 612,164, filed on 19 December 2023, which are incorporated herein by reference in their entirety.

[0002] This disclosure relates to fluorine-free hydrophobic permeable materials. This disclosure further relates to fluorine-free hydrophobic permeable films. [Background technology]

[0003] Many enclosed structures require venting to the outside atmosphere to release exhaust gases or reduce pressure differences. Venting may be necessary as a result of temperature fluctuations, changes in altitude, and the vapor pressure of the contained liquids. Vents, or venting media, equalize pressure by allowing gases to flow while repelling liquids and solids to protect internal components. Water-repellent vents and venting media may have hydrophobic surfaces. Typically, such hydrophobic surfaces are achieved by using fluorinated chemical coatings. Further improvements with permeable hydrophobic materials are desirable. [Overview of the Initiative] [Means for solving the problem]

[0004] According to one embodiment, the article comprises a permeable material having a surface; and a hydrophobic coating on the surface forming a hydrophobic surface, wherein the hydrophobic coating is fluorine-free, and the hydrophobic surface has a water contact angle of 95 degrees or greater.

[0005] According to one embodiment, the permeable film includes a permeable material having a surface, and a hydrophobic coating on the surface that forms a hydrophobic surface, wherein the hydrophobic coating is fluorine-free, and the hydrophobic surface has a water contact angle of 95 degrees or greater.

[0006] According to one embodiment, the permeable film comprises a permeable material having a surface; and a hydrophobic coating on the surface forming a hydrophobic surface, wherein the hydrophobic coating is fluorine-free, and the hydrophobic surface exhibits a wettability of 0.96 or less, 0.95 or less, 0.94 or less, 0.93 or less, 0.92 or less, 0.91 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, and 0.5 or less with a liquid having a surface tension of 35 mN / m or greater.

[0007] According to one embodiment, the vent comprises a permeable material having a surface; and a hydrophobic coating on the surface forming a hydrophobic surface, wherein the hydrophobic coating is fluorine-free, and the hydrophobic surface has a water contact angle of 95 degrees or greater.

[0008] According to one embodiment, the vented cap comprises a cap configured for use on a container; and a vent disposed within the cap, the vent comprising a permeable material having a surface; and a hydrophobic coating on the surface forming a hydrophobic surface, the hydrophobic coating being fluorine-free, and the hydrophobic surface having a water contact angle of 95 degrees or greater.

[0009] A hydrophobic surface may have a water contact angle of 100 degrees or greater, 105 degrees or greater, 110 degrees or greater, 120 degrees or greater, 130 degrees or greater, 135 degrees or greater, 140 degrees or greater, 145 degrees or greater, or 150 degrees or greater. A hydrophobic surface may exhibit a roll-off angle of 20 degrees or less, 15 degrees or less, 10 degrees or less, 8 degrees or less, or 5 degrees or less. A hydrophobic surface, in contact with a liquid having a surface tension of 35 mN / m or greater, may exhibit a wettability of 0.96 or less, 0.95 or less, 0.94 or less, 0.93 or less, 0.92 or less, 0.91 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.45 or less, or 0.4 or less. A hydrophobic surface, in contact with a liquid having a surface tension of 40 mN / m or greater, may exhibit a wettability of 0.96 or less, 0.95 or less, 0.94 or less, 0.93 or less, 0.92 or less, 0.91 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.35 or less, 0.3 or less, 0.25 or less, or 0.2 or less.

[0010] According to one embodiment, the permeable material may include a phase inversion membrane. The permeable material may include cellulose acetate, PES, or a combination thereof. The hydrophobic coating may include siloxanes, such as polyalkylsiloxanes, such as polydimethylsiloxanes. According to one embodiment, the article, permeable membrane, or vent is fluorine-free.

[0011] According to one embodiment, an article includes a permeable material having a surface; and a hydrophobic coating on the surface that forms a hydrophobic surface, the hydrophobic coating being fluorine-free, and the hydrophobic surface having a water contact angle in the range of 95 degrees to 115 degrees and a wetting rate in the range of 0.75 to 0.95 when contacting a liquid having a surface tension of 35 mN / m or greater. The permeable material may include PES. The hydrophobic coating may include polyalkylsiloxane. The hydrophobic coating may include polydimethylsiloxane.

[0012] According to one embodiment, a vent includes a permeable material having a surface; and a hydrophobic coating on the surface that forms a hydrophobic surface, the hydrophobic coating being fluorine-free, and the hydrophobic surface having a water contact angle in the range of 95 degrees to 115 degrees and a wetting rate in the range of 0.75 to 0.95 when contacting a liquid having a surface tension of 35 mN / m or greater. The permeable material may include PES. The hydrophobic coating may include polyalkylsiloxane. The hydrophobic coating may include polydimethylsiloxane.

[0013] According to one embodiment, a vented cap includes a cap configured for use on a container; and a vent disposed within the cap, the vent including a permeable material having a surface; a hydrophobic coating on the surface that forms a hydrophobic surface, the hydrophobic coating being fluorine-free, and the hydrophobic surface having a water contact angle in the range of 95 degrees to 115 degrees and a wetting rate in the range of 0.75 to 0.95 when contacting a liquid having a surface tension of 35 mN / m or greater. The permeable material may include PES. The hydrophobic coating may include polyalkylsiloxane. The hydrophobic coating may include polydimethylsiloxane.

[0014] A method of making a hydrophobic article includes adhering a hydrophobic material onto a permeable material and curing the hydrophobic material to form a hydrophobic surface. The hydrophobic material is fluorine-free, and the hydrophobic surface has a water contact angle of 120 degrees or greater. The hydrophobic material can be adhered by dip coating or chemical vapor deposition. The hydrophobic material can be adhered in the form of an emulsion containing the hydrophobic material. Curing the hydrophobic material can include crosslinking the hydrophobic material.

[0015] The above summary of the disclosure is not intended to describe each disclosed embodiment or every implementation of the disclosure. The following description, to be more specific, illustrates exemplary embodiments. Throughout this application, guidance is provided through lists of examples, which can be used in various combinations. In each case, the listed lists serve only as representative groups and should not be construed as exclusive lists.

Brief Description of the Drawings

[0016] [Figure 1A] A scanning electron microscope (SEM) image of a hydrophobic permeable material. [Figure 1B] A schematic close-up view of the material of FIG. 1A. [Figure 2] A schematic view of a container including a vented cap according to one embodiment. [Figure 3A] A SEM image of a coated medium according to an example. [Figure 3B] A SEM image of a coated medium according to an example. [Figure 3C] A SEM image of a coated medium according to an example. [Figure 3D] A SEM image of a coated medium according to an example. [Figure 3E] A SEM image of a coated medium according to an example. [Figure 3F] A SEM image of a coated medium according to an example. [Figure 4A] This is a graph display of the data from Example 1. [Figure 4B] This is a graph display of the data from Example 1. [Figure 4C] This is a graph display of the data from Example 1. [Figure 5A] This is a graph display of the data from Example 1. [Figure 5B] This is a graph display of the data from Example 1. [Figure 5C] This is a graph display of the data from Example 1. [Figure 6A] This is a graph display of the data from Example 1. [Figure 6B] This is a graph display of the data from Example 1. [Figure 6C] This is a graph display of the data from Example 1. [Figure 7] This is a graph display of the data from Example 1. [Figure 8] This is a graph display of the data from Example 3. [Modes for carrying out the invention]

[0017] definition All scientific and technical terms used herein have their common meanings in the art unless otherwise specified. The definitions provided herein are for the purpose of facilitating the understanding of certain terms that are frequently used herein and are not intended to limit the scope of this disclosure.

[0018] Unless otherwise specified, the terms “polymer” and “polymer material” include, but are not limited to, organic homopolymers, copolymers, such as block, graft, random, and alternating copolymers, terpolymers, and blends and modifications thereof. Furthermore, unless otherwise specifically limited, the term “polymer” includes all possible geometric stereostructures of the material. These stereostructures include, but are not limited to, isotactic, syndiotactic, and atactic symmetry.

[0019] In this disclosure, the term “aromatic ring” is used to refer to a conjugated ring system of an organic compound. An aromatic ring may contain only carbon atoms, or it may contain one or more heteroatoms, such as oxygen, nitrogen, or sulfur.

[0020] The term "alkylation" is used in this disclosure to describe a compound that reacts to replace a hydrogen atom or negative charge of a compound with an alkyl group such that the alkyl group is covalently bonded to the compound.

[0021] The term “alkyl” is used in this disclosure to describe monovalent groups that are the groups of alkanes, and includes linear, branched, cyclic, and bicyclic alkyl groups, as well as combinations thereof, including both unsubstituted and substituted alkyl groups. Unless otherwise indicated, alkyl groups typically contain 1 to 30 carbon atoms. In some embodiments, alkyl groups contain 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, or 1 to 3 carbon atoms. Examples of alkyl groups, but not limited to, include methyl, ethyl, n-propyl, n-butyl, n-pentyl, isobutyl, t-butyl, isopropyl, n-octyl, n-heptyl, ethylhexyl, cyclopentyl, cyclohexyl, and cycloheptyl.

[0022] The term "hydrophobic" is used herein to refer to a material property in which a material has a water contact angle greater than 90°, while a "hydrophilic" material is defined as a material with a water contact angle less than 90°. A material may be called "superhydrophobic" if it has a water contact angle of 150° or greater. Hydrophobicity and hydrophilicity can be measured by measuring the water contact angle of a material using the ASTM D7334-08R22 test method, or by using an automated contact angle tester and the ASTM D5725-99 test method. The term "wetting" is used herein to refer to a material that allows a liquid to spread evenly over its surface. Wetting can be measured using the same water contact angle test method.

[0023] The term "conformal" is used herein to refer to a coating that conforms to the surface irregularities of the underlying layer, and therefore the coating is present across the entire surface regardless of surface roughness or defects. The term "non-conformal" refers to a coating that does not conform to the surface irregularities of the underlying layer and is not present across the entire surface regardless of surface roughness or defects.

[0024] The term “substantially” can be understood to have the same meaning as “significantly” as used herein, and to modify the following term by at least about 90%, at least about 95%, or at least about 98%. The term “substantially absent” of a particular compound means that the composition of the present invention contains less than parts per million (ppm) of the listed compound. The term “absent” of a particular compound means that the composition of the present invention contains less than 20 billion (ppb) of the listed compound. In connection with the above phrases, the composition of the present invention contains less than the above amounts of the compound, whether the compound itself exists in an unreacted form or has reacted with one or more other materials.

[0025] The term "substantial" can be understood as having the same meaning as "not significant" as used herein, and as the opposite of "substantial," that is, modifying the following term by 25%, 10%, 5%, or 2% or less.

[0026] The term "approximately" is used herein in conjunction with numerical values ​​and is understood to include the normal variation in measurement that a person skilled in the art would expect, and to have the same meaning as "generally," and to cover a typical error limit, e.g., ±5% of the stated value.

[0027] Terms such as "a," "an," and "the" are not intended to refer only to singular entities, but include general classes for which specific examples may be used.

[0028] The terms "a," "an," and "the" are used interchangeably with the term "at least one." The phrases "at least one of" and "including at least one of," and the lists that follow them, refer to any one item in the list and any combination of two or more items in the list.

[0029] As used herein, the term "or" is generally used in its ordinary sense, including "and / or," unless the context clearly indicates otherwise. The term "and / or" means one or all of the elements listed, or any combination of two or more of the elements listed.

[0030] An enumeration of numerical ranges by an endpoint includes all numbers contained within that range (for example, 1-5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc., or 10 or less includes 10, 9.4, 7.6, 5, 4.3, 2.9, 1.62, 0.3, etc.). If a range of values ​​is "up to" or "at least" a specific value, that value is included within that range.

[0031] As used herein, “having,” “having,” “including,” “including,” “containing,” and “containing” are used in their unrestricted sense and generally mean “including, but not limited to, the following.” “Being essentially from,” and “consisting of,” are understood to be encompassed by “including,” etc. As used herein, “being essentially from,” when it relates to compositions, products, methods, etc., means that the components of the composition, product, method, etc., are limited to the listed components, as well as any other components that do not materially affect the basic and novel features (plural) of the composition, product, method, etc.

[0032] The words “preferred” and “preferred” refer to embodiments that may provide certain advantages under specific circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the enumeration of one or more preferred embodiments does not mean that other embodiments are not useful or that they are not intended to be excluded from the scope of this disclosure, including the claims.

[0033] The directions referred to herein, such as “top,” “bottom,” “left,” “right,” “upper,” “lower,” and other directions and orientations, are described herein for clarity in relation to the figures and do not limit the actual device or system, or the use of the device or system. The device or system may be used in several directions and orientations as described herein.

[0034] This disclosure relates to a permeable material having a fluorine-free hydrophobic coating. The material may be superhydrophobic due to the hydrophobic coating. The hydrophobic permeable material can be used in a variety of articles. Such articles may include vents used in vented caps.

[0035] In some cases, permeable hydrophobic materials are required. For example, such a material that can be permeable to gases, such as air, may be hydrophobic and therefore cannot be moistened with water. Such a material may be substantially impermeable to water.

[0036] According to one embodiment, the article comprises a permeable material having a surface, and a hydrophobic coating on the surface forming a hydrophobic surface. The hydrophobic coating is fluorine-free. Furthermore, the entire article may be fluorine-free. The hydrophobic surface exhibits a water contact angle of 120 degrees or greater. The permeable material may be a film having a first main surface and a second main surface on the opposite side. The hydrophobic coating may be attached to the surface of the film. The hydrophobic coating may be attached over the entire film such that the hydrophobic coating coats the main surface and microsurfaces, including the surface of the film or fibers and / or pores and voids.

[0037] According to one embodiment, the vent comprises a permeable material having a surface. A hydrophobic coating is disposed on the permeable material forming a hydrophobic surface. The hydrophobic coating is fluorine-free. The hydrophobic surface exhibits a water contact angle of 120 degrees or greater. The permeable material may be a film. The vent may be used in a vented cap. The vented cap comprises a cap configured for use on a container and a vent disposed within the cap. The vent may form the liquid-facing surface of the vented cap.

[0038] The permeability of a material can be measured by measuring its Frazier permeability as described in ASTM D737-18, using a Frazier permeability tester available from Frazier Precision Instrument Co., Inc., Gaithersburg, Maryland. The unit for Frazier permeability is 1 cfm / ft at a 0.5-inch water pressure drop. 2 This is 0.5 cm at 125 Pa. 3 / s / cm 2 This is equivalent to a Frazier permeability reading occurring at a 0.5-inch water pressure drop. Highly porous materials generally have high Frazier permeability, while lowly porous materials generally have low Frazier permeability. Methods for measuring pore size are described in ASTM D6767-21.

[0039] A hydrophobic coating can be used to coat any suitable permeable material. The permeable material can be selected to have a desired level of permeability. For example, the permeable material may have a pore size of at least about 0.05 μm and a permeability of 0.05 cfm / ft at a water pressure drop of 0.5''. 2 (0.025cm at 125Pa) 3 / s / cm 2 ) or greater Frazier permeability may be present. Hydrophobic (coated) permeable materials have a permeability of 0.1 cfm / ft 2 (0.051cm at 125Pa) 3 / s / cm2 ) or greater, 0.2 cfm / ft 2 (0.10 cm at 125 Pa 3 / s / cm 2 ) or greater, 0.4 cfm / ft 2 (0.20 cm at 125 Pa 3 / s / cm 2 ) or greater, 0.5 cfm / ft 2 (0.25 cm at 125 Pa 3 / s / cm 2 ) or greater, 0.6 cfm / ft 2 (0.30 cm at 125 Pa 3 / s / cm 2 ) or greater, 0.7 cfm / ft 2 (0.36 cm at 125 Pa 3 / s / cm 2 ) or greater, 0.8 cfm / ft 2 (0.41 cm at 125 Pa 3 / s / cm 2 ) or greater, 0.9 cfm / ft 2 (0.46 cm at 125 Pa 3 / s / cm 2 ) or greater, or 1 cfm / ft 2 (0.51 cm at 125 Pa 3 / s / cm 2 ) may exhibit a Frazier permeability greater than or equal to this value. In fact, there is no desirable upper limit for the permeability of the material, while the Frazier permeability of the patterned material is 3 cfm / ft 2 (1.52 cm at 125 Pa 3 / s / cm 2 ) or less, 2.5 cfm / ft 2 (1.27 cm at 125 Pa 3 / s / cm 2 ) or less, or 2 cfm / ft 2 (1.02 cm at 125 Pa 3 / s / cm 2) or lower. The hydrophobic permeable material may have at least 50%, at least 60%, at least 70%, or at least 80% of the permeability of the permeability of the permeability of the permeability of the permeability material without the hydrophobic coating.

[0040] According to one embodiment, the permeable material is coated with a fluorine-free hydrophobic coating. When a permeable material having a nanoscale or microscale surface structure is combined with a hydrophobic coating, high hydrophobicity, including superhydrophobicity, can be achieved without the use of fluorinated chemicals, such as longer-chain perfluoroalkyl substances (PFAS).

[0041] According to one embodiment, any suitable fluorine-free hydrophobic coating may be used. In some embodiments, the hydrophobic coating comprises a siloxane, for example, a polyalkylsiloxane. An example of a suitable polyalkylsiloxane is polydimethylsiloxane (PDMS). In some embodiments, the hydrophobic coating comprises an alkylated polymer, for example, an alkylated poly(meth)acrylate. Examples of suitable alkylated polymers include poly(hexyl methacrylate), poly(octyl methacrylate), and the like.

[0042] The hydrophobic permeable materials of this disclosure are particularly suitable for applications in which the material comes into contact with water or aqueous solutions. In some cases, the hydrophobic permeable materials are used as vents. Such vents may be used, for example, in packaging for aqueous solutions (e.g., in vented caps).

[0043] According to one embodiment, the hydrophobic permeable material has a hydrophobic surface exhibiting a water contact angle of 95 degrees or greater, 100 degrees or greater, 105 degrees or greater, 110 degrees or greater, 120 degrees or greater, 130 degrees or greater, 135 degrees or greater, 140 degrees or greater, 145 degrees or greater, or 150 degrees or greater. In some embodiments, the hydrophobic permeable material is superhydrophobic with a water contact angle of 150 degrees or greater. In some embodiments, the hydrophobic permeable material has a water contact angle of 160 degrees or less, 150 degrees or less, 140 degrees or less, 130 degrees or less, 120 degrees or less, or 110 degrees or less.

[0044] According to one embodiment, a hydrophobic permeable material exhibits a desirable roll-off angle when in contact with water or an aqueous solution. The roll-off angle can be measured using a contact angle meter (e.g., a goniometer). The roll-off angle may be 20 degrees or less, 15 degrees or less, 10 degrees or less, 8 degrees or less, or 5 degrees or less. The lowest possible roll-off angle may be desirable. However, in practice, the roll-off angle may be 1 degree or greater, 2 degrees or greater, or 5 degrees or greater. The roll-off angle may be in the range of 1 to 20 degrees, 1 to 15 degrees, 1 to 10 degrees, or 1 to 5 degrees.

[0045] The properties of a hydrophobic surface can also be characterized by determining the wetting rate of the surface when exposed to a liquid. The wetting rate can be calculated from the contact angle, as described in the examples below. According to one embodiment, the hydrophobic surface exhibits a wetting rate of 0.96 or less, 0.95 or less, 0.94 or less, 0.93 or less, 0.92 or less, 0.91 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.3 or less, 0.25 or less, or 0.2 or less. The wetting rate of the hydrophobic permeable material may be 0.05 or greater, 0.1 or greater, 0.2 or greater, 0.3 or greater, 0.5 or greater, 0.6 or greater, 0.7 or greater, 0.75 or greater, 0.8 or greater, 0.82 or greater, 0.84 or greater, or 0.86 or greater. The wetting rate may be within the range of 0.05-0.5, 0.1-0.5, 0.1-0.4, 0.1-0.3, 0.1-0.2, 0.2-0.96, 0.2-0.95, 0.3-0.95, 0.4-0.95, 0.5-0.95, 0.6-0.95, 0.7-0.95, or 0.8-0.95.

[0046] Permeable materials that can be used to prepare the hydrophobic permeable materials of this disclosure include, for example, membranes made of polypropylene, polyethylene, polyester, polysulfone, polyethersulfone (PES), polyamide (nylon), polyacrylonitrile, polycarbonate, or cellulose acetate. In some embodiments, the permeable material is a membrane made of cellulose acetate or polyethersulfone (PES).

[0047] In some embodiments, the permeable material is made of polyethersulfone (PES) and coated with polydimethylsiloxane (PDMS). The hydrophobic permeable material may be a polyethersulfone (PES) film coated with polydimethylsiloxane (PDMS). The film may be prepared by phase inversion. In some embodiments, the hydrophobic permeable material is a polyethersulfone (PES) film coated with polydimethylsiloxane (PDMS) and has a wettability of 0.96 or less, 0.95 or less, 0.94 or less, 0.93 or less, or 0.92 or less. The wettability of the hydrophobic permeable material may be 0.75 or greater, 0.8 or greater, 0.82 or greater, 0.84 or greater, or 0.86 or greater. The wettability of the hydrophobic permeable material may be in the range of 0.8-0.96, 0.75-0.95, 0.80-0.95, 0.82-0.95, or 0.84-0.94. In some embodiments, the hydrophobic permeable material is a polyethersulfone (PES) film coated with polydimethylsiloxane (PDMS) and has a water contact angle of 95 degrees or greater, 100 degrees or greater, or 105 degrees or greater. The water contact angle of the hydrophobic permeable material may be 120 degrees or less, 115 degrees or less, or 110 degrees or less. The water contact angle of the hydrophobic permeable material may be in the range of 95 degrees to 120 degrees, 95 degrees to 115 degrees, or 100 degrees to 110 degrees.

[0048] The permeable material may include secondary structures, such as hierarchical structures, raised pattern features, or other structures. The secondary structure may be inherent in the material or can be attached to the material by imprinting, etching, or other methods. The secondary structure may spread throughout the material (including its surface) or be positioned on the surface of the material. Such secondary structures can alter surface properties in various ways. For example, the secondary structure can alter the omniphobic surface properties of droplets (e.g., hydrophobicity, oleophobicity, etc.), (increased or decreased) adhesion, antifouling behavior, and roll-off behavior. In some embodiments, the permeable material is a phase-reversal film.

[0049] In some embodiments, the permeable material is a membrane made of a phase-inverted cellulose acetate membrane. The phase-inverted cellulose acetate membrane may have nanometer-scale spheres or clumps on micrometer-scale fibers. In some embodiments, the permeable material is a foamed membrane or material. Examples of foamed membranes and materials include foamed polyolefins, such as foamed polyethylene and foamed polypropylene. In some embodiments, the permeable material includes raised pattern features on its surface. A permeable material having raised pattern features is described in international application PCT / US2022 / 023143 to Yoder et al.

[0050] According to one embodiment, the permeable material has an outer surface having a hierarchical pattern including a plurality of microscale features (e.g., clumps) and a plurality of raised macroscale features formed on the outer surface. The terms “microscale” and “macroscale” are used to distinguish features that differ by at least an order of magnitude in size, with microscale being understood to be smaller than macroscale. In this context, the terms “microscale” and “macroscale” do not necessarily indicate any particular size range. The permeable material may further include features of intermediate sizes between microscale and macroscale features, or features that are smaller or larger than either microscale or macroscale features. In some embodiments, the permeable material itself has a hierarchical structure, and another layer of hierarchy is added to the porous material by forming raised macroscale features. For example, cellulose acetate may have clumps that are about 50 nm to 1000 nm in size, and pores that are about 0.2 μm to 20 μm (or possibly up to 50 μm), and raised structures formed on the cellulose acetate may be up to 60 μm in size.

[0051] A hydrophobic, permeable material can be part of a composite material. A composite material can be a multilayer material. A hydrophobic, permeable material can form the outermost layer(s) of a composite material. Further layers(s) of a composite material can also be permeable.

[0052] The hydrophobic coating can be deposited onto a porous material by any suitable method. In some embodiments, the hydrophobic coating is deposited onto a permeable material by dip coating or chemical vapor deposition. The deposition ratio can be selected to achieve the desired hydrophobicity and / or roll-off angle. The deposition ratio can be selected to achieve the desired residual permeability. In some embodiments, the hydrophobic permeable material includes a hydrophobic coating in amounts of 0.5% or more, 1% or more, 2% or more, 3% or more, 4% or more, or 5% or more, based on the total weight of the coated material. The hydrophobic coating can consist of 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, or 3% or less, based on the total weight of the coated hydrophobic permeable material.

[0053] According to one embodiment, a method for producing a hydrophobic article includes attaching a hydrophobic material to a permeable material and curing the hydrophobic material to form a hydrophobic surface. The hydrophobic material can be attached by dip coating the permeable material into a coating composition containing the hydrophobic material, or by chemical vapor deposition.

[0054] Hydrophobic materials can be provided in coating compositions. Hydrophobic materials can be applied in the form of an emulsion containing the hydrophobic material. The emulsion may contain the hydrophobic material in an aqueous carrier and optionally one or more surfactants. Examples of suitable aqueous carriers include water, and mixtures of water and organic solvents, such as ethanol, isopropanol, and butanol. Examples of suitable surfactants include alkylating acids, such as lauric acid and palmitic acid.

[0055] The concentration of the coating composition may affect the permeability of the coated material. In some embodiments, the concentration of the coating composition (e.g., emulsion) may be selected to achieve a desired level of hydrophobicity and permeability. Higher concentrations may result in increased hydrophobicity and decreased permeability. In some cases, the coating composition is applied at a concentration that maintains at least 50%, at least 60%, at least 70%, or at least 80% of the initial permeability of the underlying permeable material. In some embodiments, some permeability may be traded for hydrophobicity, but by using the methods and materials of the present disclosure, it is possible to achieve a water contact angle of 140 degrees or greater while maintaining 80% or more of the initial permeability. The hydrophobic material may be included in the emulsion at concentrations of 6 w / v% or less, 5 w / v% or less, 4.5 w / v% or less, 4 w / v% or less, 3.5 w / v% or less, 3 w / v% or less, or 2.5 w / v% or less. Hydrophobic materials may be included in the emulsion at concentrations of 0.25 w / v% or higher, 0.5 w / v% or higher, 0.75 w / v% or higher, 1 w / v% or higher, 1.5 w / v% or higher, or 2 w / v% or higher. Exemplary concentration ranges of hydrophobic materials in the emulsion include 0.25 w / v% to 6 w / v%, 0.5 w / v% to 5 w / v%, 0.5 w / v% to 4 w / v%, 1 w / v% to 4 w / v%, and 1 w / v% to 3 w / v%.

[0056] Emulsions can be characterized by their droplet size (sometimes referred to as particle size). The droplet size of an emulsion can be measured by methods used for particle size measurement, such as dynamic light scattering. Emulsions may have droplet sizes of 0.1 μm or larger, 0.2 μm or larger, 0.5 μm or larger, or 1 μm or larger. Emulsions may have droplet sizes of 10 μm or smaller, 8 μm or smaller, or 5 μm or smaller. Droplet sizes may range from 0.1 μm to 10 μm, 0.1 μm to 8 μm, or 0.2 μm to 5 μm.

[0057] A method for applying a hydrophobic coating may further include removing water or an aqueous solvent from the coating composition (e.g., an emulsion) after the coating composition has been applied to the surface. The water or aqueous solvent may be removed from the coating composition at a raised temperature. For example, the temperature of the coating composition may be raised to 50°C or higher, 75°C or higher, 100°C or higher, or 120°C or higher. The temperature of the coating composition may be raised up to 200°C, 175°C, or 150°C. The water or aqueous solvent may be removed from the coating composition by maintaining a high temperature for an appropriate period of time. For example, the high temperature may be maintained for 1 minute or longer, 2 minutes or longer, 3 minutes or longer, 4 minutes or longer, or 5 minutes or longer. The high temperature may be maintained for 30 minutes or less, 20 minutes or less, 15 minutes or less, or 10 minutes or less. Furthermore, curing of the hydrophobic material may occur during or after the removal of water.

[0058] Curing a hydrophobic material may involve crosslinking the hydrophobic material. In some cases, hydrophobic materials can self-crosslink. However, in many cases, the coating composition (e.g., emulsion) contains a crosslinking agent. Examples of suitable crosslinking agents include tetramethyl orthosilicate, tetraethyl orthosilicate, and acid catalysts (suitable for crosslinking by condensation); as well as Pt catalysts for crosslinking via vinyl groups (if present) in the hydrophobic material. The crosslinking agent may be included in any suitable concentration depending on the chemical properties of the crosslinking agent and the hydrophobic material, and the desired degree of crosslinking. Curing of the hydrophobic material may occur at higher temperatures. A specific temperature may be selected based on the chemical properties of the hydrophobic material and the optionally selected crosslinking agent. Some materials can be cured at lower temperatures, e.g., 25°C to 50°C. Other materials may benefit from higher temperatures, e.g., 50°C or higher, 75°C or higher, 100°C or higher, 120°C or higher, or 140°C or higher. The curing temperature is preferably below the temperature at which the hydrophobic material or the underlying permeable material undergoes thermal decomposition. For example, the hydrophobic material may be cured (e.g., crosslinked) at temperatures below 250°C, below 225°C, below 200°C, or below 175°C.

[0059] The hydrophobic coating prepared by this method results in a hydrophobic surface exhibiting a water contact angle of 95 degrees or greater, 100 degrees or greater, 105 degrees or greater, 110 degrees or greater, 120 degrees or greater, 130 degrees or greater, 135 degrees or greater, 140 degrees or greater, 145 degrees or greater, or 150 degrees or greater. The hydrophobic coating prepared by this method results in a hydrophobic surface exhibiting a roll-off angle of 20 degrees or less, 15 degrees or less, 10 degrees or less, 8 degrees or less, or 5 degrees or less. The lowest possible roll-off angle may be desirable. However, in practice, the roll-off angle may be 1 degree or greater, 2 degrees or greater, or 5 degrees or greater. The roll-off angle may be in the range of 1 to 20 degrees, 1 to 15 degrees, 1 to 10 degrees, or 1 to 5 degrees.

[0060] The deposition of hydrophobic materials by the methods described herein may result in the formation of a conformal hydrophobic coating on a permeable material. The conformal hydrophobic coating exhibits hydrophobicity due to the hydrophobic properties of the hydrophobic material. The conformal hydrophobic coating may also exhibit increased hydrophobicity due to the surface structure of the underlying permeable material. Such increased hydrophobicity can be achieved, in particular, by permeable materials having secondary or hierarchical structures (e.g., microscale features, e.g., small clumps) on their surface. Examples of such materials include phase inversion films, as discussed elsewhere in this specification. The conformal hydrophobic coating can make materials with secondary structures hydrophobic and even superhydrophobic, even when the underlying material may itself be hydrophilic.

[0061] According to embodiments, the hydrophobic surface of a hydrophobic material produced by the method of the present disclosure is fluorine-free. The hydrophobic material can be further produced into suitable articles. An example of an article produced from the hydrophobic material is a vent, for example, a vent on a bottle cap. A vent produced from the hydrophobic material is fluorine-free and allows for the venting of gases from a container (e.g., a bottle) while exhibiting water resistance. A vent produced from the hydrophobic material may also exhibit a desirable level of chemical resistance and can be used in bottle caps for chemical storage bottles.

[0062] Referring to Figure 1A, an SEM image of an exemplary hydrophobic permeable material 1 is shown. In the exemplary hydrophobic permeable material 1, the permeable material is a phase-inverted cellulose acetate film 10. A schematic representation of a part of the hydrophobic permeable material 1 is shown in Figure 1B. The hydrophobic coating 11 forms a conformal coating on the cellulose acetate film 10. That is, the cellulose acetate film 10 is coated with the hydrophobic coating 11 on all sides, including around the fibrous portions and within the pores and voids.

[0063] Figure 2 schematically illustrates an exemplary container 30 (e.g., a bottle) and a cap 20 configured to close the opening 31 of the container 30. The cap 20 is a vented cap and includes a vent 21 made of a hydrophobic porous material according to embodiments of the present disclosure.

[0064] Exemplary Embodiments The technology described herein is defined in the claims. However, a non-exclusive list of non-limiting embodiments is provided below. Any one or more features of these embodiments may be combined with any one or more features of other examples, embodiments, or aspects described herein.

[0065] Embodiment 1 is, Permeable material having a surface; and Hydrophobic coating on a surface that forms a hydrophobic surface The article contains a hydrophobic coating that is fluorine-free, and the hydrophobic surface has a water contact angle of 95 degrees or greater.

[0066] Embodiment 2 is the article of Embodiment 1, wherein the hydrophobic surface has a water contact angle of 100 degrees or greater, 105 degrees or greater, 110 degrees or greater, 120 degrees or greater, 130 degrees or greater, 135 degrees or greater, 140 degrees or greater, 145 degrees or greater, or 150 degrees or greater. The hydrophobic surface may have a water contact angle of 160 degrees or less, 150 degrees or less, 140 degrees or less, 130 degrees or less, 120 degrees or less, or 110 degrees or less.

[0067] Embodiment 3 is the article of Embodiment 1 or 2, wherein the hydrophobic surface exhibits a roll-off angle of 20 degrees or less, 15 degrees or less, 10 degrees or less, 8 degrees or less, or 5 degrees or less.

[0068] Embodiment 4 is an article of any one of Embodiments 1 to 3, wherein the hydrophobic surface, in contact with a liquid having a surface tension of 35 mN / m or greater, exhibits a wettability of 0.96 or less, 0.95 or less, 0.94 or less, 0.93 or less, 0.92 or less, 0.91 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.45 or less, or 0.4 or less. The hydrophobic surface may exhibit a wettability of 0.05 or greater, 0.1 or greater, 0.2 or greater, 0.3 or greater, 0.4 or greater, 0.5 or greater, 0.6 or greater, 0.7 or greater, or 0.8 or greater.

[0069] Embodiment 5 is an article of any one of Embodiments 1 to 4, wherein the hydrophobic surface, in contact with a liquid having a surface tension of 40 mN / m or greater, exhibits a wettability of 0.96 or less, 0.95 or less, 0.94 or less, 0.93 or less, 0.92 or less, 0.91 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.35 or less, 0.3 or less, 0.25 or less, or 0.2 or less. A hydrophobic surface may exhibit a wettability of 0.05 or greater, 0.1 or greater, 0.2 or greater, 0.3 or greater, 0.4 or greater, 0.5 or greater, 0.6 or greater, 0.7 or greater, 0.75 or greater, or 0.8 or greater.

[0070] Embodiment 6 is an article of any one of Embodiments 1 to 5, wherein the permeable material includes a phase reversal film.

[0071] Embodiment 7 is an article of any one of Embodiments 1 to 6, and its surface exhibits a small-lump secondary structure.

[0072] Embodiment 8 is an article of any one of Embodiments 1 to 7, wherein the permeable material includes cellulose acetate, PES, or a combination thereof.

[0073] Embodiment 9 is an article from any one of Embodiments 1 to 8, and the hydrophobic coating is crosslinked.

[0074] Embodiment 10 is an article of any one of Embodiments 1 to 9, wherein the hydrophobic coating comprises a siloxane, optionally comprising a polyalkylsiloxane, and further optionally comprising a polydimethylsiloxane.

[0075] Embodiment 11 is an article from any one of Embodiments 1 to 10, wherein the hydrophobic coating comprises an alkylated polymer, for example, poly(hexyl methacrylate), poly(octyl methacrylate), or a combination thereof.

[0076] Embodiment 12 is an article from any one of Embodiments 1 to 11, wherein the hydrophobic coating is applied to the permeable material by dip coating or chemical vapor deposition.

[0077] Embodiment 13 is an article from any one of Embodiments 1 to 12, and the article is fluorine-free.

[0078] Embodiment 14 is, Permeable material having a surface; and Hydrophobic coating on a surface that forms a hydrophobic surface The permeable film contains a hydrophobic coating that is fluorine-free and has a water contact angle of 95 degrees or greater.

[0079] Embodiment 15 is, Permeable material having a surface; and Hydrophobic coating on a surface that forms a hydrophobic surface The permeable film contains a hydrophobic coating that is fluorine-free, and the hydrophobic surface exhibits a wettability of 0.5 or less when exposed to a liquid with a surface tension of 35 mN / m or greater.

[0080] Embodiment 16 is a permeable film of Embodiment 14 or 15, wherein the hydrophobic surface has a water contact angle of 100 degrees or greater, 105 degrees or greater, 110 degrees or greater, 120 degrees or greater, 130 degrees or greater, 135 degrees or greater, 140 degrees or greater, 145 degrees or greater, or 150 degrees or greater. The hydrophobic surface may have a water contact angle of 160 degrees or less, 150 degrees or less, 140 degrees or less, 130 degrees or less, 120 degrees or less, or 110 degrees or less.

[0081] Embodiment 17 is a permeable film according to any one of Embodiments 14 to 16, wherein the hydrophobic surface exhibits a roll-off angle of 20 degrees or less, 15 degrees or less, 10 degrees or less, 8 degrees or less, or 5 degrees or less.

[0082] Embodiment 18 is a permeable film according to any one of Embodiments 14 to 17, wherein the hydrophobic surface, in contact with a liquid having a surface tension of 35 mN / m or greater, exhibits a wettability of 0.96 or less, 0.95 or less, 0.94 or less, 0.93 or less, 0.92 or less, 0.91 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.45 or less, or 0.4 or less. The hydrophobic surface may exhibit a wettability of 0.05 or greater, 0.1 or greater, 0.2 or greater, 0.3 or greater, 0.4 or greater, 0.5 or greater, 0.6 or greater, 0.7 or greater, 0.75 or greater, or 0.8 or greater.

[0083] Embodiment 19 is a permeable film according to any one of Embodiments 14 to 18, wherein the hydrophobic surface, in contact with a liquid having a surface tension of 40 mN / m or greater, exhibits a wettability of 0.96 or less, 0.95 or less, 0.94 or less, 0.93 or less, 0.92 or less, 0.91 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.35 or less, 0.3 or less, 0.25 or less, or 0.2 or less. A hydrophobic surface may exhibit a wettability of 0.05 or greater, 0.1 or greater, 0.2 or greater, 0.3 or greater, 0.4 or greater, 0.5 or greater, 0.6 or greater, 0.7 or greater, 0.75 or greater, or 0.8 or greater.

[0084] Embodiment 20 is a permeable film according to any one of Embodiments 14 to 19, wherein the permeable material includes a phase inversion film.

[0085] Embodiment 21 is a permeable film according to any one of Embodiments 14 to 20, and its surface exhibits a small-lump secondary structure.

[0086] Embodiment 22 is a permeable membrane according to any one of Embodiments 14 to 21, wherein the permeable material includes cellulose acetate, PES, or a combination thereof.

[0087] Embodiment 23 is a permeable film according to any one of Embodiments 14 to 22, and the hydrophobic coating is crosslinked.

[0088] Embodiment 24 is a permeable film according to any one of Embodiments 14 to 23, wherein the hydrophobic coating comprises a siloxane, optionally comprising a polyalkylsiloxane, and further optionally comprising a polydimethylsiloxane.

[0089] Embodiment 25 is a permeable film according to any one of Embodiments 14 to 24, wherein the hydrophobic coating includes an alkylated polymer, such as poly(hexyl methacrylate), poly(octyl methacrylate), or a combination thereof.

[0090] Embodiment 26 is a permeable film according to any one of Embodiments 14 to 25, and the hydrophobic coating is attached to the permeable material by dip coating or chemical vapor deposition.

[0091] Embodiment 27 is a permeable membrane according to any one of Embodiments 14 to 26, and the permeable membrane is fluorine-free.

[0092] Embodiment 28 is, Permeable material having a surface; and Hydrophobic coating on a surface that forms a hydrophobic surface The vent contains a hydrophobic coating that is fluorine-free, and the hydrophobic surface has a water contact angle of 95 degrees or greater.

[0093] Embodiment 29 is the vent of Embodiment 28, wherein the hydrophobic surface has a water contact angle of 100 degrees or greater, 105 degrees or greater, 110 degrees or greater, 120 degrees or greater, 130 degrees or greater, 135 degrees or greater, 140 degrees or greater, 145 degrees or greater, or 150 degrees or greater. The hydrophobic surface may have a water contact angle of 160 degrees or less, 150 degrees or less, 140 degrees or less, 130 degrees or less, 120 degrees or less, or 110 degrees or less.

[0094] Embodiment 30 is a vent of Embodiment 28 or 29, wherein the hydrophobic surface exhibits a roll-off angle of 20 degrees or less, 15 degrees or less, 10 degrees or less, 8 degrees or less, or 5 degrees or less.

[0095] Embodiment 31 is a vent from any one of Embodiments 28 to 30, wherein the hydrophobic surface, in contact with a liquid having a surface tension of 35 mN / m or greater, exhibits a wettability of 0.96 or less, 0.95 or less, 0.94 or less, 0.93 or less, 0.92 or less, 0.91 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.45 or less, or 0.4 or less. The hydrophobic surface may exhibit a wettability of 0.05 or greater, 0.1 or greater, 0.2 or greater, 0.3 or greater, 0.4 or greater, 0.5 or greater, 0.6 or greater, 0.7 or greater, 0.75 or greater, or 0.8 or greater.

[0096] Embodiment 32 is a vent from any one of Embodiments 28 to 31, wherein the hydrophobic surface, in contact with a liquid having a surface tension of 40 mN / m or greater, exhibits a wettability of 0.96 or less, 0.95 or less, 0.94 or less, 0.93 or less, 0.92 or less, 0.91 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.35 or less, 0.3 or less, 0.25 or less, or 0.2 or less. A hydrophobic surface may exhibit a wettability of 0.05 or greater, 0.1 or greater, 0.2 or greater, 0.3 or greater, 0.4 or greater, 0.5 or greater, 0.6 or greater, 0.7 or greater, 0.75 or greater, or 0.8 or greater.

[0097] Embodiment 33 is a vent from any one of Embodiments 28 to 32, and the permeable material includes a phase inversion membrane.

[0098] Embodiment 34 is a vent from any one of Embodiments 28 to 33, and its surface exhibits a small-lump secondary structure.

[0099] Embodiment 35 is a vent from any one of Embodiments 28 to 34, wherein the permeable material includes cellulose acetate, PES, or a combination thereof.

[0100] Embodiment 36 is a vent from any one of Embodiments 28 to 35, and the hydrophobic coating is crosslinked.

[0101] Embodiment 37 is a vent from any one of Embodiments 28 to 36, wherein the hydrophobic coating comprises a siloxane, optionally comprising a polyalkylsiloxane, and further optionally comprising a polydimethylsiloxane.

[0102] Embodiment 38 is a vent from any one of Embodiments 28 to 37, and the hydrophobic coating comprises an alkylated polymer, for example, poly(hexyl methacrylate), poly(octyl methacrylate), or a combination thereof.

[0103] Embodiment 39 is a vent from any one of Embodiments 28 to 38, and the hydrophobic coating is attached to the permeable material by dip coating or chemical vapor deposition.

[0104] Embodiment 40 is one of the vents from Embodiments 28 to 39, and the vent is fluorine-free.

[0105] Embodiment 41 is, A cap designed for use on a container; and Vents located inside the cap It is a vented cap that includes The vent is A permeable material having a surface; Hydrophobic coating on a surface that forms a hydrophobic surface The hydrophobic coating contains fluorine-free material, and the hydrophobic surface has a water contact angle of 95 degrees or greater.

[0106] Embodiment 42 is a vented cap of Embodiment 41, wherein the hydrophobic surface has a water contact angle of 100 degrees or greater, 105 degrees or greater, 110 degrees or greater, 120 degrees or greater, 130 degrees or greater, 135 degrees or greater, 140 degrees or greater, 145 degrees or greater, or 150 degrees or greater. The hydrophobic surface may have a water contact angle of 160 degrees or less, 150 degrees or less, 140 degrees or less, 130 degrees or less, 120 degrees or less, or 110 degrees or less.

[0107] Embodiment 43 is a vented cap of Embodiment 41 or 42, wherein the hydrophobic surface exhibits a roll-off angle of 20 degrees or less, 15 degrees or less, 10 degrees or less, 8 degrees or less, or 5 degrees or less.

[0108] Embodiment 44 is a vented cap of any one of Embodiments 41 to 43, wherein the hydrophobic surface, in contact with a liquid having a surface tension of 35 mN / m or greater, exhibits a wettability of 0.96 or less, 0.95 or less, 0.94 or less, 0.93 or less, 0.92 or less, 0.91 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.45 or less, or 0.4 or less. The hydrophobic surface may exhibit a wettability of 0.05 or greater, 0.1 or greater, 0.2 or greater, 0.3 or greater, 0.4 or greater, 0.5 or greater, 0.6 or greater, 0.7 or greater, 0.75 or greater, or 0.8 or greater.

[0109] Embodiment 45 is a vented cap of any one of Embodiments 41 to 44, wherein the hydrophobic surface, in contact with a liquid having a surface tension of 40 mN / m or greater, exhibits a wettability of 0.96 or less, 0.95 or less, 0.94 or less, 0.93 or less, 0.92 or less, 0.91 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.35 or less, 0.3 or less, 0.25 or less, or 0.2 or less. A hydrophobic surface may exhibit a wettability of 0.05 or greater, 0.1 or greater, 0.2 or greater, 0.3 or greater, 0.4 or greater, 0.5 or greater, 0.6 or greater, 0.7 or greater, 0.75 or greater, or 0.8 or greater.

[0110] Embodiment 46 is a vented cap according to any one of Embodiments 41 to 45, wherein the permeable material includes a phase inversion membrane.

[0111] Embodiment 47 is a vented cap from any one of Embodiments 41 to 46, and its surface exhibits a small-lump secondary structure.

[0112] Embodiment 48 is a vented cap of any one of Embodiments 41 to 47, wherein the permeable material includes cellulose acetate, PES, or a combination thereof.

[0113] Embodiment 49 is a vented cap from any one of Embodiments 41 to 48, and the hydrophobic coating is crosslinked.

[0114] Embodiment 50 is a vented cap of any one of Embodiments 41 to 49, wherein the hydrophobic coating comprises a siloxane, optionally comprising a polyalkylsiloxane, and further optionally comprising a polydimethylsiloxane.

[0115] Embodiment 51 is a vented cap of any one of Embodiments 41 to 50, wherein the hydrophobic coating comprises an alkylated polymer, such as poly(hexyl methacrylate), poly(octyl methacrylate), or a combination thereof.

[0116] Embodiment 52 is a vented cap of any one of Embodiments 41 to 51, wherein the hydrophobic coating is applied to the permeable material by dip coating or chemical vapor deposition.

[0117] Embodiment 53 is a vented cap according to any one of Embodiments 41 to 52, wherein the vent is fluorine-free.

[0118] Embodiment 54 is a method for producing a hydrophobic article, and the method is: Deposition of a hydrophobic material onto a permeable material; The process involves curing hydrophobic materials to form a hydrophobic surface. The hydrophobic material contains fluorine-free material, and its hydrophobic surface has a water contact angle of 95 degrees or greater.

[0119] Embodiment 55 is the method of Embodiment 54, in which a hydrophobic material is attached by dip coating or chemical vapor deposition.

[0120] Embodiment 56 is the method of Embodiment 54 or 55, wherein the hydrophobic material is attached in the form of an emulsion containing the hydrophobic material.

[0121] Embodiment 57 is one of the methods from Embodiments 54 to 56, wherein the emulsion comprises an aqueous carrier and optionally one or more surfactants.

[0122] Embodiment 58 is one of the methods from Embodiments 54 to 57, wherein curing the hydrophobic material includes crosslinking the hydrophobic material.

[0123] Embodiment 59 is one of the methods from Embodiments 54 to 58, further comprising adhering a hydrophobic material to a surface and then removing water from the hydrophobic material, optionally, the removal of water being performed at a raised temperature.

[0124] Embodiment 60 is one of the methods from Embodiments 54 to 59, in which curing occurs during or after the removal of water.

[0125] Embodiment 61 is one of the methods of Embodiments 54 to 60, wherein the hydrophobic material comprises a siloxane, optionally comprising a polyalkylsiloxane, and further optionally comprising a polydimethylsiloxane.

[0126] Embodiment 62 is one of the methods of Embodiments 54 to 61, wherein the hydrophobic material includes alkylated polymers, such as poly(hexyl methacrylate), poly(octyl methacrylate), or a combination thereof.

[0127] Embodiment 63 is one of the methods of Embodiments 54 to 62, wherein the hydrophobic surface has a water contact angle of 100 degrees or greater, 105 degrees or greater, 110 degrees or greater, 120 degrees or greater, 130 degrees or greater, 135 degrees or greater, 140 degrees or greater, 145 degrees or greater, or 150 degrees or greater. The hydrophobic surface may have a water contact angle of 160 degrees or less, 150 degrees or less, 140 degrees or less, 130 degrees or less, 120 degrees or less, or 110 degrees or less.

[0128] Embodiment 64 is one of the methods of Embodiments 54 to 63, wherein the hydrophobic surface exhibits a roll-off angle of 20 degrees or less, 15 degrees or less, 10 degrees or less, 8 degrees or less, or 5 degrees or less.

[0129] Embodiment 65 is one of the methods of Embodiments 54 to 64, wherein the hydrophobic surface, in contact with a liquid having a surface tension of 35 mN / m or greater, exhibits a wettability of 0.96 or less, 0.95 or less, 0.94 or less, 0.93 or less, 0.92 or less, 0.91 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.45 or less, or 0.4 or less. The hydrophobic surface may exhibit a wettability of 0.05 or greater, 0.1 or greater, 0.2 or greater, 0.3 or greater, 0.4 or greater, 0.5 or greater, 0.6 or greater, 0.7 or greater, 0.75 or greater, or 0.8 or greater.

[0130] Embodiment 66 is one of the methods of Embodiments 54 to 65, wherein the hydrophobic surface, upon contact with a liquid having a surface tension of 40 mN / m or greater, exhibits a wettability of 0.96 or less, 0.95 or less, 0.94 or less, 0.93 or less, 0.92 or less, 0.91 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.35 or less, 0.3 or less, 0.25 or less, or 0.2 or less. A hydrophobic surface may exhibit a wettability of 0.05 or greater, 0.1 or greater, 0.2 or greater, 0.3 or greater, 0.4 or greater, 0.5 or greater, 0.6 or greater, 0.7 or greater, 0.75 or greater, or 0.8 or greater.

[0131] Embodiment 67 is one of the methods from Embodiments 54 to 66, wherein the permeable material includes a phase inversion film.

[0132] Embodiment 68 is one of the methods of Embodiments 54 to 67, and the surface exhibits a small-lump secondary structure.

[0133] Embodiment 69 is one of the methods described in Embodiments 54 to 68, wherein the permeable material includes cellulose acetate, PES, or a combination thereof.

[0134] Embodiment 70 is one of the methods of Embodiments 54 to 69, wherein the permeable material has initial permeability before the hydrophobic material is attached to the permeable material, and after the hydrophobic material is attached to the permeable material, the permeable material has final permeability, the final permeability being at least 50%, at least 60%, at least 70%, or at least 80% of the initial permeability.

[0135] Embodiment 71 is one of the methods from Embodiments 54 to 70, wherein the hydrophobic article includes a film.

[0136] Embodiment 72 is one of the methods from Embodiments 54 to 71, wherein the hydrophobic article includes a vent. [Examples]

[0137] Media prepared from various materials, including cellulose acetate (CA), foamed PTFE (ePTFE), and polyethersulfone (PES), as well as commercially available composite media (SYNTEQ XP®), were coated using the method of this disclosure.

[0138] The coated materials (medium samples A-J) with those nominal pore sizes are shown in Table 1A below:

[0139] [Table 1]

[0140] As detailed in Table 1B below, the coatings were prepared using various commercially available polydimethylsiloxane (PDMS) coating materials, while the comparative coating was prepared using a fluorinated C6 polymer:

[0141] [Table 2]

[0142] Coating of the medium sample The concentrated emulsion of the coating was diluted to 3% (w / v) with distilled water (18.3 MOhm). Comparative coating 3 was dissolved in Novec 7100 solvent. The diluted coating material was then placed in a Petri dish (approximately 4'' in diameter and 0.5'' in depth). The media samples to be coated had a diameter of 90 mm or less. Holding the media with tweezers, it was drawn into the emulsion from one side of the Petri dish to the other, and then removed from the emulsion. Excess emulsion was drained while holding the media vertically. The media was placed between two square aluminum frames (3'' × 4'') bound together with a paper binder. This was then placed in an oven at 150°C for 5 minutes to dry / cur. Before testing, the media was removed from the frames. Only the portion of the media that was not in contact with the frames was used for testing.

[0143] Several scanning electron microscope (SEM) images of coated samples are shown in Figure 3A (medium B with coating 8); 3B (medium C with coating 1); 3C (medium D with coating 1); 3D (medium E with coating 3); 3E (medium F with coating 3); and 3F (medium G with coating 1).

[0144] The weight increase of media A and B due to coatings 1 and 2 was also determined. The coating weights are shown in Table 1C below.

[0145] [Table 3]

[0146] Example 1 The contact angle and wetting rate of media A to G coated with coatings 1 to 3 were determined.

[0147] contact angle measurement The contact angles of test solutions with various known surface tension levels were measured as follows (the test method reflects ASTM D2578). Deionized water (18.2 MOhm) was used for the test at a surface tension of 72 mN / m. For all other surface tensions, ACCUDYNE TEST® surface tension test solutions were used, formulated from 100% reagent-grade materials according to ASTM D2578.

[0148] Five 10 μL droplets of liquid with known surface tension were gently placed onto a coated medium sample. Contact angles were measured using a DROPMASTER DM-701 contact angle meter with a tilting stage (available from Kyowa Interface Science Co., Ltd., Niiza City, Japan). The surface tension of each of the five droplets was measured, and the average was reported.

[0149] The wettness rate was calculated from the contact angle θ (theta) using Equation 1.

number

number

[0150] x values ​​greater than 1 are not considered valid and are not shown on the plot (maximum Y range of 1.0).

[0151] The results are shown in Figures 4A (Coating 1 on media A and B), 4B (Coating 1 on media C and D), 4C (Coating 1 on media G); Figures 5A (Coating 2 on media A and B), 5B (Coating 2 on media C and D), 5C (Coating 2 on media G); and Figures 6A (Coating 3 on media A and B), 6B (Coating 3 on media C and D), 6C (Coating 3 on media G). Figure 7 shows media B coated with coating 2, and media B, F, and E coated with comparative coating 3.

[0152] Example 2 Samples of media A-D, F, and H were coated with coatings 1-3 as described in Example 1, and the Frazier permeability of the samples was determined as described in ASTM D737-18 using a Frazier permeability tester available from Frazier Precision Instrument Co., Inc., Gaithersburg, Maryland. To measure permeability for small pore size membranes, the pressure was doubled from 125 to 250 psi to help obtain readings. The thus obtained permeability measurements were then divided by 10 to obtain the Frazier permeability. The porosity of the media samples was measured by the water-exclusion porosity assay (WEP).

[0153] WEP measurement A specialized apparatus was used for WEP measurement. The apparatus consists of two plates with a media sample sandwiched between them. The upper plate contains six 6.35 mm openings, allowing for six separate measurements. Beneath each media sample is a tube filled with distilled water and connected to a manometer equipped with a pressure control valve. The starting air pressure was 1 psi and was slowly increased by 1 psi every 45 seconds. As soon as water was observed above the media sample in the opening (upper on the atmospheric pressure side), the pressure was recorded as the result of the WEP.

[0154] The results for permeability and porosity are shown in Tables 2A and 2B, respectively.

[0155] [Table 4]

[0156] [Table 5]

[0157] Example 3 Samples of media I and J were coated with coatings 1, 2, 7, and 8 as described in Example 1, and the contact angle and Frazier permeability were determined as described in Examples 1 and 2. The results (including the retention of permeability of the coated media) are shown in Tables 3A (Medium I) and 3B (Medium J) below.

[0158] [Table 6]

[0159] [Table 7]

[0160] Example 4 The effect of emulsion particle viscosity on permeability was evaluated by coating a medium sample (medium H) with coatings (coatings 4-6) exhibiting different levels of emulsion particle viscosity. The viscosity of the emulsion particles was reported by the supplier (CHT Group). Coating compositions were also prepared with different concentrations of emulsion. Emulsion particle size (emulsion droplet diameter) was measured by dynamic light scattering. Particle sizes ranged from 215 nm to 260 nm.

[0161] The permeability results are shown in Figure 8. It was observed that low-viscosity PDMS or uncured PDMS could easily coat pores up to about 5 weight percent, with only moderate loss of permeability. It was further observed that PDMS viscosity had a greater influence on permeability retention than particle size. As long as the viscosity was low (e.g., before curing), large-particle emulsions did not clog smaller pores.

[0162] All references and published materials cited herein are expressly incorporated by reference in their entirety, unless they would directly contradict this disclosure. While specific embodiments have been illustrated and described herein, those skilled in the art will recognize that various alternative and / or equivalent implementations can be used in place of the specific embodiments shown and described without departing from the scope of this disclosure. This disclosure is not intended to be unduly limited by the exemplary embodiments and examples described herein, and such examples and examples are presented together with the scope of this disclosure, which is intended to be limited only by the claims set forth herein as merely examples.

Claims

1. Articles, Permeable material having a surface; and A hydrophobic coating on the surface that forms a hydrophobic surface An article comprising the above, wherein the hydrophobic coating is fluorine-free, and the hydrophobic surface has a water contact angle of 95 degrees or greater.

2. The article according to claim 1, wherein the hydrophobic surface has a water contact angle of 100 degrees or greater, 105 degrees or greater, 110 degrees or greater, 120 degrees or greater, 130 degrees or greater, 135 degrees or greater, 140 degrees or greater, 145 degrees or greater, 150 degrees or greater, or in the range of 95 degrees to 115 degrees.

3. The article according to claim 1 or 2, wherein the hydrophobic surface exhibits a roll-off angle of 20 degrees or less, 15 degrees or less, 10 degrees or less, 8 degrees or less, or 5 degrees or less.

4. The article according to any one of claims 1 to 3, wherein the hydrophobic surface, upon contact with a liquid having a surface tension of 35 mN / m or greater, exhibits a wettability of 0.96 or less, 0.95 or less, 0.94 or less, 0.93 or less, 0.92 or less, 0.91 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.45 or less, or 0.4 or less, or in the range of 0.75 to 0.

95.

5. The article according to any one of claims 1 to 4, wherein the hydrophobic surface, upon contact with a liquid having a surface tension of 40 mN / m or greater, exhibits a wettability of 0.96 or less, 0.95 or less, 0.94 or less, 0.93 or less, 0.92 or less, 0.91 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.35 or less, 0.3 or less, 0.25 or less, or 0.2 or less.

6. The article according to any one of claims 1 to 5, wherein the permeable material includes a phase reversal film, and optionally the surface exhibits a small-clump secondary structure.

7. The article according to any one of claims 1 to 6, wherein the permeable material comprises cellulose acetate, PES, or a combination thereof.

8. The article according to any one of claims 1 to 7, wherein the hydrophobic coating is crosslinked.

9. The article according to any one of claims 1 to 8, wherein the hydrophobic coating comprises a siloxane, optionally comprising a polyalkylsiloxane, and optionally comprising a polydimethylsiloxane.

10. An article according to any one of claims 1 to 9, which is a permeable membrane.

11. The article according to any one of claims 1 to 10, wherein the permeable film has a hydrophobic surface that exhibits a wettability of 0.5 or less when exposed to a liquid having a surface tension of 35 mN / m or greater.

12. Permeable material having a surface; and A hydrophobic coating on the surface that forms a hydrophobic surface A vent comprising a hydrophobic coating which is fluorine-free, and the hydrophobic surface which has a water contact angle of 95 degrees or greater.

13. The vent according to claim 12, wherein the hydrophobic surface has a water contact angle of 100 degrees or greater, 105 degrees or greater, 110 degrees or greater, 120 degrees or greater, 130 degrees or greater, 135 degrees or greater, 140 degrees or greater, 145 degrees or greater, 150 degrees or greater, or in the range of 95 degrees to 115 degrees.

14. The vent according to claim 12 or 13, wherein the hydrophobic surface exhibits a roll-off angle of 20 degrees or less, 15 degrees or less, 10 degrees or less, 8 degrees or less, or 5 degrees or less.

15. The vent according to any one of claims 12 to 14, wherein the hydrophobic surface, upon contact with a liquid having a surface tension of 35 mN / m or greater, exhibits a wettability of 0.96 or less, 0.95 or less, 0.94 or less, 0.93 or less, 0.92 or less, 0.91 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.45 or less, or 0.4 or less, or in the range of 0.75 to 0.

95.

16. The vent according to any one of claims 12 to 15, wherein the hydrophobic surface, upon contact with a liquid having a surface tension of 40 mN / m or greater, exhibits a wettability of 0.96 or less, 0.95 or less, 0.94 or less, 0.93 or less, 0.92 or less, 0.91 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.35 or less, 0.3 or less, 0.25 or less, or 0.2 or less.

17. The vent according to any one of claims 12 to 16, wherein the permeable material includes a phase reversal film.

18. The vent according to any one of claims 12 to 17, wherein the surface exhibits a small-clump secondary structure.

19. The vent according to any one of claims 12 to 18, wherein the permeable material comprises cellulose acetate, PES, or a combination thereof.

20. The vent according to any one of claims 12 to 19, wherein the hydrophobic coating is crosslinked.

21. The vent according to any one of claims 12 to 20, wherein the hydrophobic coating comprises a siloxane, optionally comprising a polyalkylsiloxane, and optionally comprising a polydimethylsiloxane.

22. A vent according to any one of claims 12 to 21, which is fluorine-free.

23. A cap designed for use on a container; and The vent according to any one of claims 12 to 22 A vented cap, including [a specific feature / feature].

24. Adhering a hydrophobic material to a permeable material; The hydrophobic material is cured to form a hydrophobic surface. A method for producing a hydrophobic article, comprising: The method wherein the hydrophobic material is fluorine-free, and the hydrophobic surface has a water contact angle of 95 degrees or greater.

25. The method according to claim 24, wherein the hydrophobic material is attached by dip coating or chemical vapor deposition.

26. The method according to claim 24 or 25, wherein the hydrophobic material is attached in the form of an emulsion containing the hydrophobic material.

27. The method according to any one of claims 24 to 26, wherein the emulsion comprises an aqueous carrier and optionally one or more surfactants.

28. The method according to any one of claims 23 to 27, wherein the curing of the hydrophobic material includes crosslinking the hydrophobic material.

29. The method according to any one of claims 23 to 28, wherein the hydrophobic material comprises a siloxane, optionally the hydrophobic coating comprises a polyalkylsiloxane, and optionally the hydrophobic coating comprises a polydimethylsiloxane.

30. The method according to any one of claims 23 to 29, wherein the hydrophobic surface has a water contact angle of 100 degrees or greater, 105 degrees or greater, 110 degrees or greater, 120 degrees or greater, 130 degrees or greater, 135 degrees or greater, 140 degrees or greater, 145 degrees or greater, 150 degrees or greater, or in the range of 95 degrees to 115 degrees.

31. The method according to any one of claims 23 to 30, wherein the hydrophobic surface exhibits a roll-off angle of 20 degrees or less, 15 degrees or less, 10 degrees or less, 8 degrees or less, or 5 degrees or less.

32. The method according to any one of claims 23 to 31, wherein the hydrophobic surface, upon contact with a liquid having a surface tension of 35 mN / m or greater, exhibits a wettability of 0.96 or less, 0.95 or less, 0.94 or less, 0.93 or less, 0.92 or less, 0.91 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.45 or less, or 0.4 or less, or in the range of 0.75 to 0.

95.

33. The method according to any one of claims 23 to 32, wherein the hydrophobic surface, upon contact with a liquid having a surface tension of 40 mN / m or greater, exhibits a wettability of 0.96 or less, 0.95 or less, 0.94 or less, 0.93 or less, 0.92 or less, 0.91 or less, 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.35 or less, 0.3 or less, 0.25 or less, or 0.2 or less.

34. The method according to any one of claims 23 to 33, wherein the permeable material includes a phase reversal film.

35. The method according to any one of claims 23 to 34, wherein the surface exhibits a small-clump secondary structure.

36. The method according to any one of claims 23 to 35, wherein the permeable material comprises cellulose acetate, PES, or a combination thereof.

37. The method according to any one of claims 23 to 36, wherein, before the hydrophobic material is attached to the permeable material, the permeable material has an initial permeability, and after the hydrophobic material is attached to the permeable material, the permeable material has a final permeability, the final permeability being at least 50%, at least 60%, at least 70%, or at least 80% of the initial permeability.

38. The method according to any one of claims 23 to 37, wherein the hydrophobic article includes a film.

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