• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    SUPER-HYDROPHOBIC SURFACES The present invention relates to a surface of a substrate, or the substrate itself, exhibiting super-hydrophobic characteristics when treated with a formulation comprising a hydrophobic component, nanostructured particles and water. Superhydrophobicity can be applied either over the entire surface, shaped by all or the substrate material, and / or directly penetrated through the directional thickness z of the substrate material.
    公开号:BR112014000770B1
    申请号:R112014000770-5
    申请日:2012-06-18
    公开日:2021-03-16
    发明作者:Jian Qin；Donald E. Waldroup；Constantine M. Megaridis；Thomas M. Schutzius；Ilker S. Bayer
    申请人:Kimberly-Clark Worldwide, Inc；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    [001] The present invention relates to surfaces that exhibit superhydrophobic properties when treated with a composition made of water-based non-organic solvent. BACKGROUND OF THE INVENTION
    [002] A super-hydrophobic surface exhibits a sessile contact angle with water greater than 150 °. If, in addition, the surface has a water droplet roll (slide) angle of less than 10 °, the surface is considered "self-cleaning". In nature, lotus leaves exhibit such properties (called the "lotus effect"). Most synthetic materials, such as fabrics, nonwovens, cellulose fabrics, polymeric films, etc., do not have surfaces with such properties. Currently, there are two methods for modifying the non-superhydrophobic surface to achieve the lotus effect. One method is to graft a hydrophobic monomer onto the entire surface of a non-hydrophobic material. This method makes the material super-hydrophobic through the thickness of the material, which may not be desirable in most cases. It is also unprofitable, cannot be used for continuous production, and can lead to undesirable environmental problems. Another approach is to coat a specially formulated liquid dispersion on a surface, and after subsequent drying, a super-hydrophobic nanostructured film is formed. In order to use such an approach, the deposited film must exhibit a chemical and physical morphology characteristic of the superhydrophobic surfaces. First, the formulation requires at least a low-surface (i.e., hydrophobic) energy component, such as a perfluorinated polymer (eg, polytetrafluoroethylene), and second, the treated surface must have a rough surface texture. , preferably in various micro and nanorugostic length scales. Although there are several formulated dispersions capable of reaching a hydrophobic surface, none of these dispersions appear to be solely water-based. For a large number of safety, health, economic and environmental issues, it is also important that the dispersion is entirely water based, when considering production on a commercial scale, as this will decrease the issues associated with the use of organic solvents. . SUMMARY OF THE INVENTION
    [003] The present invention relates to a superhydrophobic surface consisting of a substrate treated with a composition comprising: (A) a hydrophobic component, (b) nanostructured particles and (c) water. BRIEF DESCRIPTION OF THE FIGURES FIG. 1 shows a porous non-wettable substrate, resistant to water penetration, due to its small pore size and high hydrophobicity (high contact angle, θ). FIG. 2 shows the (hydrostatic) penetration pressures of the mixture of water and water + isopropyl alcohol (IPA) for a meltblown, melted and blown hydrophobic substrate (Sample 1), and a hydrophilic cellulose-based substrate (Sample 4), both coated with an aqueous fluorochemical dispersion, PMC (trade name Capstone ST-100, fluorinated acrylic copolymer, 20% by weight in water, obtained from DuPont). There are no nanostructured particles in this formulation, where the coating mass per unit area is> 10g / m2. FIG. 3 (a) shows a three-dimensional confocal microscope image of a hydrophobic substrate, fused and blown, which has been dyed with a dye for fluorescence visualization. FIG. 3 (b) shows the vacuum fraction of a molten and blown hydrophobic substrate as a function of substrate depth for the untouched substrate (open and uncoated squares) and for the same substrate with a hydrophobic coating (open circles). . 3 (c) shows the vacuum fraction of a spunbond substrate (continuous heat-welded filaments) as a function of substrate depth for the untouched substrate (open and uncoated squares) and for the same substrate with a hydrophobic coating (open circles). FIG. 3 (d) shows the vacuum fraction of a Kimberly-Clark® Towel as a function of substrate depth of the untouched substrate (open and uncoated squares) and for the same substrate with a hydrophobic coating (open circles). FIG. 4 (a) shows the technique of measuring sessile contact angle. The coating texture is visible. FIG. 4 (b) shows water droplet beads resting on a substrate coated with KC Hydroknit®. FIG. 5 (a) shows the hydrostatic pressure of five different samples after being coated with a formulation at a coating level of 13.7 g / m2. FIG. 5 (b) shows the hydrostatic pressure of five different samples after being coated with a formulation at a coating level of 27.4 g / m2. FIGs. 6 (a) and 6 (b) show the hydrostatic pressure of two different samples. Tests were performed with two test liquids. FIG. 7 shows the hydrostatic pressure of two different samples after being coated with a formulation at a coating level of 78.4 g / m2. FIG. 8 shows the hydrostatic pressure of two samples coated with a formulation at a rate of 47 g / m2. FIG. 9 shows the hydrostatic pressure of two samples coated with different formulations. The coating levels were the minimum necessary for the accumulation of water, but it did not guarantee measurable water penetration pressures. DETAILED DESCRIPTION OF THE INVENTION
    [004] All percentages are by weight of the total composition, unless specifically stated otherwise. All proportions are proportions by weight, unless specifically stated otherwise.
    [005] The term "super-hydrophobic" refers to the property of a surface in repelling water very effectively. This property is quantified by a water contact angle greater than 150 °.
    [006] The term "hydrophobic", as used herein, refers to the property of a water repelling surface, with a water contact angle of about 90 ° to about 120 °.
    [007] The term "hydrophilic", as used herein, refers to surfaces with angles of contact with water well below 90 °.
    [008] The term "self-cleaning", as used herein, refers to the property of repelling water, with the angle of water rolling over a sloping surface being less than 10 °.
    [009] As used herein, the term "non-woven blanket" or "technical fabric" means a blanket that has a structure of individual fibers or filaments, which are intertwined, but not identifiable, such as a knitted fabric. Nonwoven blankets were formed from various processes, such as, for example, meltblowing processes (casting and blowing), spunbonding processes (continuous heat-sealed filaments), airflow processes, coform® processes (manufacturing process of absorbent material composed of cellulose and molten polymers injected in hot air) and blanket by carding and consolidation by pressure and heat. The base weight of nonwoven blankets is usually expressed in ounces of material per square yard (osy) or grams per square meter (gsm) and the diameters of the fibers are usually expressed in microns, or in the case of cut fibers, denier. Note that to convert osy to gsm, multiply osy by 33.91.
    [010] As used herein, the term "fibers formed by heat-sealed continuous filaments" refers to small diameter fibers of the molecularly oriented polymeric material. Fibers formed by continuous heat-sealed filaments can be formed by extrusion of molten thermoplastic material, such as fibers from a plurality of thin and generally circular capillaries with the diameter of the extruded fibers, and then being rapidly reduced, for example, in U.S. Patent No. 4,340,563 to Appel et al., and in U.S. Patent No. 3,692,618 to Dorschner et al., in US Patent No. 3,802,817 to Matsuki et al., in US Patent No. 3,338,992 and 3,341,394 to Kinney, in U.S. Patent No. 3,502,763 to Hartman, in U.S. Patent No. 3,542,615 to Dobo et al., And in U.S. Patent No. 5,382,400 to Pike et al. Fibers formed by continuous heat-sealed filaments are generally not sticky when deposited on a collecting surface and are generally continuous. Fibers formed by continuous heat-sealed filaments often have a diameter of 10 microns or more. However, blankets of fine fibers formed by continuous heat-welded filaments (which have an average fiber diameter of less than about 10 microns) can be obtained through a variety of methods, including, but not limited to, those described in the commonly assigned U.S. Patent, N °. 6,200,669 to Marmon et al. and US Patent. No. 5,759,926 to Pike et al.
    [011] The "meltblown" nonwoven blanket is made from melted and blown fibers. As used herein, the term "meltblown fibers" means fibers formed by extruding a thermoplastic material melted through a plurality of thin capillaries, usually circular and fused, such as strands or filaments melted in gas streams (eg air) at high speed, usually hot, which attenuates the filaments of the molten thermoplastic material to reduce its diameter, which can be up to the diameter of the microfiber. Thereafter, the "meltblown" fibers are driven by the high-speed gas flow and are deposited on a collecting surface to form a blanket of randomly dispersed fused fibers. Such a process is described, for example, in the U.S. Patent. No. 3,849,241 to Buntin. Meltblown fibers are microfibers, which can be continuous or discontinuous, usually smaller than 10 microns in diameter (using a sample size of at least 10), and generally sticky when deposited on a collecting surface.
    [012] As used herein, the term "polymer" generally includes, but is not limited to, homopolymers, copolymers, such as, for example, copolymers, block, graft, random and alternate terpolymers, etc., and mixtures and modifications thereof. In addition, unless otherwise specifically limited, the term "polymer" should include all possible geometric configurations of the molecule. These configurations include, but are not limited to, isotactic, syndiotactic and random symmetries.
    [013] As used herein, the term "multi-component fibers" refers to fibers or filaments that have been formed from at least two extruded polymers from separate extruders, but spun together to form a fiber. Multi-component fibers are also sometimes referred to as "conjugated" or "bicomponent" fibers or filaments. The term "bicomponent" means that there are two polymeric components that make up the fibers. Polymers are generally different from each other, although the conjugated fibers can be prepared from the same polymer, if the polymer in each component is different from one another in some physical property, such as, for example, melting point, temperature of glass transition or the softening point. In all cases, the polymers are disposed in substantially and constantly distinct zones across the cross-section of the multi-component fibers or filaments and extend continuously along the length of the multi-component fibers or filaments. The configuration of a multi-component fiber can be, for example, a sheath / core arrangement, in which one polymer is surrounded by another, in a side-by-side arrangement, in a pie arrangement or in an "island" arrangement. Multi-component fibers are taught in U.S. Patent No. 5,108,820 to Kaneko et al .; US Patent No. 5,336,552 to Strack et al .; and U.S. Patent No. 5,382,400 to Pike et al. For bicomponent fibers or filaments, the polymers can be present in proportions of 75/25, 50/50, 25/75 or any other desired proportion.
    [014] As used herein, the term "multi-constituent fibers" refers to fibers that have been formed from at least two extruded polymers from the same extruder as a compound or mixture. Multiconstituent fibers do not have the various polymeric components in distinct zones relatively and constantly positioned across the transverse area of the fiber and the various polymers are generally not continuous along the entire length of the fiber, instead they usually form fibrils or protofibrils that begin and end up randomly. Fibers of this type are generally discussed, for example, in U.S. Patent No. 5,108,827 and 5,294,482 for Gessner.
    [015] As used herein, the term "substantially continuous fibers" is intended to mean fibers having a length that is greater than the length of the cut fibers. The term is intended to include fibers that are continuous, such as heat-sealed continuous fibers, and fibers that are not continuous, but that have a defined length greater than 150 millimeters.
    [016] As used herein, the term "continuous fibers" means that they have a fiber length generally in the range of 0.5 to about 150 millimeters. The cut fibers can be cellulosic fibers or non-cellulosic fibers. Some examples of suitable non-cellulosic fibers that can be used include, but are not limited to, polyolefin fibers, polyester fibers, nylon fibers, polyvinyl acetate fibers and mixtures thereof. Cut cellulosic fibers include, for example, pulp, thermomechanical pulp, synthetic cellulosic fibers, modified cellulosic fibers and the like. Cellulosic fibers can be obtained from secondary or recycled sources. Some examples of suitable cellulosic fiber sources include virgin wood fibers, such as thermomechanical cellulose, long fiber cellulose, bleached and raw hardwood cellulose. Secondary or recycled cellulosic fibers can be obtained from office waste, newsprint, lots of brown paper, waste cardboard, etc., can also be used. In addition, vegetable fibers, such as abaca, linen, milkweed, cotton, modified cotton, cotton linters, can also be used as cellulosic fibers. In addition, synthetic cellulosic fibers, such as, for example, rayon and rayon viscose can be used. The modified cellulosic fibers are generally composed of cellulose derivatives, formed by substituting appropriate radicals (for example, carboxyl, alkyl, acetate, nitrate, etc.) for the hydroxyl groups along the carbon chain.
    [017] As used herein, the term "cellulose" refers to fibers from natural sources such as woody and non-woody plants. Woody plants include, for example, deciduous and coniferous trees. Non-woody plants include, for example, cotton, flax, esparto, asclepias, straw, jute, hemp, and mulch.
    [018] As used herein, "fabric products" are intended to include tissue paper, bath tissue, towels, handkerchiefs, napkins and the like. The present invention is useful with tissue products and tissue paper in general, including, but not limited to, conventionally pressed felt tissue paper, densified tissue paper, and high-volume non-compacted tissue paper.
    [019] The present invention relates to a surface of a substrate, or the substrate itself, exhibiting superhydrophobic characteristics, when treated with a formulation comprising a hydrophobic component, nanostructured particles and water. Superhydrophobicity can be applied either over the entire surface, shaped over all or over the substrate, and / or directly penetrated through the directional thickness z of the substrate material.
    [020] Hydrophobic Component
    [021] The hydrophobic component is a hydrophobic polymer that is dispersible in water to form the basic elements of the superhydrophobic properties of the present invention. In general, a hydrophobic component of this invention may include, but is not limited to, fluorinated or perfluorinated polymers. However, due to the low degree of dispersibility in water, the fluorinated or perfluorinated polymer may need to be modified by the introduction of a comonomer in its molecular structure. Suitable comonomers include, but are not limited to, ethylenically unsaturated monomers comprising functional groups that can be ionized in water. An example is an ethylenically unsaturated carboxylic acid, such as acrylic acid. The amount of comonomer within the hydrophobic component is determined by the balance between two properties: hydrophobicity and dispersibility in water. An example of a hydrophobic component of the present invention is a modified perfluorinated polymer compound commercially available from DuPont as a water-based product, under the trade name Capstone® ST-100. Due to its low surface energy, the polymer not only contributes to super-hydrophobicity, but can also act as a binder to bond the nanostructured particles of the present invention to the surface. In addition, polymeric molecules can be modified to contain groups, such as amines, which can become charged by lowering the pH and altering the hydrophobicity dynamics within the liquid dispersion. In such a case, the polymer can stabilize in water through partial interaction. The surfactants that are introduced into the composition can also behave as dispersing agents for the polymer, and thus, also altering part of the hydrophobic mechanics.
    [022] The solid components of the present invention (i.e., nanostructured polymer particles) can be present in an amount of about 1.0% to about 3.0%, by weight of the solution. Such an amount is suitable for spray applications, where the higher concentrations of both polymers and / or nanostructured particles in the dispersion can lead to viscoelastic behavior, which results in spray nozzle clogging or incomplete atomization and formation of fibers. , or dramatic increases in dispersion viscosity and, consequently, nozzle clogging. It should be noted that this band is not fixed and that it is a function of the materials being used and the process used in preparing the dispersion. When a larger amount of the polymer is used, the surface structure is less desirable, as it does not have the proper texture to be hydrophobic. When a smaller amount of polymer is used, the bond is less desirable, since the coating behaves more like a removable powder coating. In addition, it is desirable that the weight ratio of polymer to particle is about 4: 1 or about 3: 2, or about 1: 1, or about 2: 3, or about 1 : 4, in order to optimize the balance between the low surface energy and the desirable surface texture.
    [023] Non-Organic Solvent
    [024] The formulation used for the surface treatment of the invention eliminates the use of an organic solvent, carefully selecting the appropriate combination of elements to grant hydrophobic characteristics. Preferably, the non-organic solvent is water. Any type of water can be used, however, demineralized or distilled water can be chosen for use during the manufacturing process for advanced features. The use of water helps to reduce the safety problems associated with the manufacture of commercial scale formulations that contain organic solvents. For example, due to the high volatility and flammability of most organic solvents, eliminating such use in the composition reduces production safety hazards. In addition, production costs can be reduced by eliminating the necessary ventilation and fire prevention equipment for organic solvents. Raw material costs can be reduced in addition to transporting materials such as an additional advantage in using the non-organic solvent formulation to achieve the present invention. In addition, since water is considered a natural resource, surfaces treated with water-based solvents can be considered healthier and better for the environment. The formulation used to treat the surface of the present invention, contains more than about 95%, more than about 98%, or about 99% water by weight of the dispersion composition.
    [025] Nanostructured particles
    [026] Nanostructured particles, which we define here as particles exhibiting repeated sizes <100 nm, are used in the present invention to achieve a desirable rough surface. The particles can be of the class of smoked silicas, hydrophobic titanium and zinc oxides and unmodified nanoargylates, as well as organically modified. Although hydrophobic particles can be used, it is desirable that the particles of the present invention are hydrophilic. If hydrophobic particles are used, the particles must be treated with a surfactant to be dispersed in water, in order to avoid agglomeration. When used, the amount of surfactant present must be kept at a low concentration, so that the desired hydrophobic properties are maintained. Therefore, the use of surfactants in the present invention should be between about 0%, or about 0.25%, or about 1.0% to no more than about 0.5%, or no more than than about 1.5% or no more than about 2%, by weight of the total composition. Such surfactants can be non-ionic, cationic or anionic in nature. Suitable anionic surfactants may include, but are not limited to, sulfonates, carboxylates and phosphates. Suitable cationic surfactants can include, but are not limited to, quaternary amines. Suitable nonionic surfactants may include, but are not limited to, block copolymers containing ethylene oxide and silicone surfactants.
    [027] Other Ingredients
    [028] Binders
    [029] The hydrophobic polymers within the formulation of the present invention play a dual role, acting as a hydrophobic and binder component. Polymers, such as Dupont's Capstone ® ST-100 promote adhesion, when compared to the fluorinated polymer alone, so that an additional binder within the composition is unnecessary. If a water-dispersible hydrophobic polymer is used when an additional binder is required, it is preferable that the binder is selected from water-dispersible acrylics, polyurethane dispersions, acrylic copolymers or acrylic polymer precursors (capable of carrying out cross-linking after coating curing).
    [030] The amount of binder present in the formulation of the present invention can vary. A binder can be included in an effective amount of up to about 2.0% by weight of the total dispersion composition.
    [031] Stabilizing agent
    [032] The formulation in the present invention can be further treated with a stabilizing agent to promote the formation of a stable dispersion when other ingredients are added to it. The stabilizing agent can be a surfactant, a polymer or mixtures thereof. If a polymer acts as a stabilizing agent, it is preferable that the polymer differs from the hydrophobic component used in the previously described base composition.
    [033] Additional stabilizing agents may include, but are not limited to, cationic surfactants, such as quaternary amines; anionic surfactants, such as sulfonates, carboxylates and phosphates; or nonionic surfactants, such as block copolymers containing ethylene oxide and silicone surfactants. Surfactants can be external or internal. External surfactants may not react chemically in the base polymer during the preparation of the dispersion. Examples of external surfactants useful here include, but are not limited to, dodecyl benzene sulfonic acid salts and lauryl sulfonic acid salt. Internal surfactants are surfactants that react chemically in the base polymer during the preparation of the dispersion. An example of an internal surfactant useful here includes dimethylol propionic acid 2.2 and its salts.
    [034] In some embodiments, the stabilizing agent used in the composition to treat the surface of the present invention can be used in an amount ranging from greater than zero to about 60%, for the hydrophobic component. For example, long-chain fatty acids or their salts can be used from about 0.5% to about 10% by weight, based on the amount of hydrophobic component. In other embodiments, ethylene-acrylic acid or ethylene-methacrylic acid copolymers can be used in an amount up to about 80%, by weight, based on the hydrophobic component. In still other embodiments, the sulfonic acid salts can be used in an amount of about 0.01% to about 60%, by weight, based on the weight of the hydrophobic component. Other mild acids, such as those of the carboxylic acid family (for example, formic acid), can also be included in order to further stabilize the dispersion. In an embodiment that includes formic acid, it can be present in an amount that is determined by the desired dispersion pH, where the pH is less than approximately 6.
    [035] Additional filling agents
    [036] The composition used to treat the surface of the present invention may further comprise one or more fillers. The composition can comprise from about 0.01 to about 600 parts, by weight, of the hydrophobic component, for example, polyolefins and the stabilizing agent. In some embodiments, the filler filler charge in the composition can be from about 0.01 to about 200 parts, by weight, of the hydrophobic component, for example, polyolefins and the stabilizing agent. It is preferred that such filler material, if used, is hydrophilic. The filler material may include conventional fillers such as ground glass, calcium carbonate, aluminum trihydrate, talc, antimony trioxide, fly ash, clays (such as bentonite or kaolin clays, for example), or other known fillers. Untreated clays and talc are generally hydrophilic in nature.
    [037] Substrate
    [038] The substrate of the present invention can be treated in such a way that it is super-hydrophobic, through the directional thickness z of the material and is controlled in such a way that only certain areas of the material are hydrophobic. Such treatment can be designed to control areas of the material that may or may not be penetrated by moisture, and thus, controlling where the liquid can flow.
    [039] Suitable substrates of the present invention can include non-woven fabric, synthetic fabric, mesh fabric or laminates of these materials. The substrate can also be a tissue or towel, as described herein. Suitable materials and processes for forming such substrates are generally well known to those skilled in the art. For example, some examples of nonwoven fabrics that can be used in the present invention include, but are not limited to, blankets, "meltblown" blankets, carded and bonded blankets, airflow blankets, coform tapirs, nonwoven blanket "spunlace", blankets hydraulically intertwined, and the like. In each case, at least one of the fibers used to prepare the nonwoven fabric is a thermoplastic material containing fiber. In addition, non-woven fabrics can be a combination of thermoplastic fibers and natural fibers, such as, for example, softwood cellulosic fibers (pulp, wood pulp, thermomechanical pulp, etc.). In general, from the point of view of cost and desired properties, the substrate of the present invention is a non-woven fabric.
    [040] If desired, the nonwoven fabric can also be bonded using techniques well known in the art to improve durability, strength, hand, aesthetics, texture, and / or other properties of the fabric. For example, non-woven fabric can be thermally bonded (for example, bonded by pattern, air-dried), ultrasonically, by gluing and / or mechanically (for example, sewn). For example, the various pattern bonding techniques are described in U.S. Patent No. 3,855,046 to Hansen; Patent no. 5,620,779 to Levy, et al .; US Patent No. 5,962,112 to Haynes, et al .; US Patent No. 6,093,665 to Sayovitz, et al ;. US Design Patent No. 428,267 to Romano, et al .; and US Design Patent No. 390,708 for Brown.
    [041] Non-woven fabric can be bonded by seamless seams or patterns. As additional examples, the nonwoven fabric can be attached along the periphery of the sheet, or simply across the width or in the transverse direction (CD) of the blanket adjacent to the edges. Other bonding techniques, such as a combination of thermal bonding and latex impregnation, can also be used. Alternatively and / or in addition, a resin, latex or adhesive can be applied to the nonwoven fabric, for example, by spraying or printing, and dried to provide the desired bond. Still other suitable bonding techniques can be described in U.S. Patent No. 5,284,703 to Everhart, et al., U.S. Patent No. 6,103,061 to Anderson, et al .; and U.S. Patent No. 6,197,404 to Varona.
    [042] In another embodiment, the substrate of the present invention is formed from a spunbonded blanket containing one-component and / or multi-component fibers. Multicomponent fibers are fibers that have been formed from at least two polymer components. Such fibers are usually extruded from separate extruders, but spun together to form a fiber. The polymers of the respective components are generally different from each other, although the multi-component fibers may include separate components of similar or identical polymeric materials. The individual components are typically disposed in distinct zones substantially and constantly positioned across the cross section of the fiber and extend substantially along the entire length of the fiber. The configuration of such fibers can be, for example, in a side-by-side arrangement, a circular arrangement, or any other arrangement.
    [043] When used, multi-component fibers can also be divisible. In the manufacture of multi-component fibers that are divisible, each of the segments that collectively form the unitary multi-component fiber is contiguous along the longitudinal direction of the multi-component fiber in such a way that one or more segments form part of the outer surface of the unitary multi-component fiber. In other words, one or more segments are exposed along the outer perimeter of the multi-component fiber. For example, divisible multi-component fibers and methods for making such fibers are described in U.S. Patent No. 5,935,883 to Pike and in U.S. Patent No. 6,200,669 to Marmon, et al.
    [044] The substrate of the present invention may also contain a "coform" material (absorbent material composed of cellulose and molten polymers injected in hot air). The term "coform material" generally refers to composite materials that comprise a stabilized mixture or matrix of thermoplastic fibers and a second non-thermoplastic material. As an example, coform® materials (absorbent material composed of cellulose and molten polymers injected in hot air) can be manufactured by a process in which at least one die and blow die head is arranged next to a chute, through which other materials are added to the mat during molding. These other materials may include, but are not limited to, organic fibrous materials, such as wood pulp and non-wood such as cotton, rayon, recycled paper, pulp down and also superabsorbent particles or fibers, inorganic absorbent materials, treated polymeric cut fibers and the like. Some examples of these coform materials are disclosed in U.S. Patent No. 4,100,324 to Anderson, et al .; US Patent No. 5,284,703 to Everhart, et al .; US Patent No. 5,350,624 to Georger, et al.
    [045] In addition, the substrate can also be formed from a material conferred with the texture of one or more surfaces. For example, in some embodiments, the substrate can be formed from a spunbond fabric or meltblown material, as described in U.S. Patent No. 4,659,609 to Lamers, et al. and U.S. Patent No. 4,833,003 to Win, et al.
    [046] In a particular embodiment of the present invention, the substrate is formed from a hydro-matted non-woven fabric. The processes of hydro entanglement and hydro-matted composite blankets containing various combinations of different types of fibers are known in the art. A typical hydro entanglement process uses high pressure water jets to entangle the fibers and / or filaments to form a highly entangled consolidated fibrous structure, for example, a nonwoven fabric. Hydro-tangle nonwoven fabrics of fibers cut to length and continuous filaments are described, for example, in U.S. Patent No. 3,494,821 to Evans and U.S. Patent No. 4,144,370. Nonwoven fabrics composed of hydro-tangled composite of a continuous filament nonwoven blanket and a layer of cellulose are disclosed, for example, in U.S. Patent No. 5,284,703 to Everhart, et al. and U.S. Patent No. 6,315,864 by Anderson et al.
    [047] Of these non-woven materials, hydro-matted non-woven blankets with cut fibers matted with thermoplastic fibers are especially suitable as a substrate. In a specific example of a hydro-matted non-woven fabric, the cut fibers are hydraulically matted with substantially continuous thermoplastic fibers. The staple can be cellulosic cut fiber, non-cellulosic cut fibers or a mixture thereof. Suitable non-cellulosic cut fibers include thermoplastic cut fibers, such as cut polyolefin fibers, cut polyester fibers, cut nylon fibers, cut fibers of polyvinyl acetate, and the like or mixtures of these materials. Suitable cellulosic cut fibers include, for example, pulp, thermomechanical pulp, synthetic cellulosic fibers, modified cellulosic fibers and the like. Cellulosic fibers can be obtained from secondary or recycled sources. Some examples of suitable cellulosic fiber sources include virgin wood fibers, such as thermomechanical cellulose, long fiber cellulose, bleached and raw hardwood cellulose. Secondary or recycled cellulosic fibers can be obtained from office waste, newsprint, lots of brown paper, waste cardboard, etc., can also be used. In addition, vegetable fibers, such as abaca, linen, asclepias, cotton, modified cotton, cotton linters, can also be used as cellulosic fibers. In addition, synthetic cellulosic fibers, such as, for example, rayon and rayon viscose can be used. The modified cellulosic fibers are generally composed of cellulose derivatives, formed by substituting appropriate radicals (for example, carboxyl, alkyl, acetate, nitrate, etc.) for the hydroxyl groups along the carbon chain.
    [048] A particularly suitable hydro-tangle non-woven fabric is a composite of non-woven material of polypropylene spunbond fibers, which are substantially continuous fibers, having hydraulically matted cellulosic fibers with the spunbond fibers. Another particularly suitable hydro-tangle non-woven fabric is a non-woven fabric composed of polypropylene spunbond fibers containing a mixture of hydraulically matted cellulosic and non-cellulosic fibers mixed with spunbond fibers.
    [049] The substrate of the present invention can be prepared exclusively from thermoplastic fibers, or it can contain both thermoplastic fibers and non-thermoplastic fibers. In general, when the substrate contains both thermoplastic and non-thermoplastic fibers, the thermoplastic fibers make up about 10% to about 90% by weight of the substrate. In a particular embodiment, the substrate contains between about 10% and about 30%, by weight, of thermoplastic fibers.
    [050] Generally, a non-woven substrate will have a base weight in the range of about 17 gsm (grams per square meter) and about 200 gsm, more typically, between about 33 gsm to about 200 gsm. The actual base weight can be over 200 gsm, but for many applications, the base weight will be in the range of 33 gsm and 150 gsm.
    [051] The thermoplastic materials or fibers that make up at least part of the substrate can be essentially any thermoplastic polymer. Suitable thermoplastic polymers include polyolefins, polyesters, polyamides, polyurethanes, polyvinyl chloride, polytetrafluoroethylene, polystyrene, polyethylene terephthalate, biodegradable polymers such as polylactic acid and copolymers and mixtures thereof. Suitable polyolefins include polyethylene, for example, high density polyethylene, medium density polyethylene, low density polyethylene and linear low density polyethylene; polypropylene, for example, isotactic polypropylene, syndiotactic polypropylene and mixtures of isotactic polypropylene and atactic polypropylene, and mixtures thereof; polybutylene, for example, poly (1-butene), and poly (2-butene); polyipentene, for example, poly (1-pentene) and poly (2-pentene), poly (3-methyl-1-pentene); poly (4-methyl-1-pentene) and copolymers and mixtures thereof. Suitable copolymers include random and block copolymers prepared from two or more distinct unsaturated olefin monomers, such as ethylene / propylene and ethylene / butylene copolymers. Suitable polyamides include nylon 6, nylon 6/6, nylon 4/6, nylon 11, nylon 12, nylon 6/10, nylon 6/12, nylon 12/12, caprolactam copolymers and alkylene oxide diamine, and the like , as well as mixtures and copolymers of these products. Suitable polyesters include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, POLYCYCLEHEXYLENE-1,4-DIMETHYLENE TEREFTALATE, isophthalate and copolymers thereof, as well as mixtures thereof. Such thermoplastic polymers can be used to prepare substantially continuous fibers and cut fibers, in accordance with the present invention.
    [052] In another embodiment, the substrate can be a tissue paper product. The tissue paper product may be of a homogeneous or multilayered construction, and the tissue paper products made of it may be of a single layer or multilayered construction. The tissue paper product desirably has a basis weight of about 10 g / m2 to about 65 g / m2, and a density of about 0.6 g / cc or less. Most desirably, the base weight will be about 40 g / m2 or less and the density will be about 0.3 g / cc or less. Most desirably, the density will be from about 0.04 g / cc to about 0.2 g / cc. Unless otherwise stated, all values and weights for the paper are on a dry basis. A tensile strength in the machine direction can be in the range of about 100 to about 5,000 grams per inch in width. A tensile strength in the machine direction can be in the range of about 50 to about 2,500 grams per inch in width. Absorbency is typically about 5 grams of water per gram of fiber to about 9 grams of water per gram of fiber.
    [053] Conventionally pressed paper products and methods of producing such products are well known in the art. Paper products are typically made by depositing a papermaking mass on a molded canvas with holes, often referred to in the art as a Fourdrinier canvas. Once the raw material is deposited on the forming screen, it is called a roll. The roll is dehydrated by pressing the web and dried at a high temperature. The particular techniques and typical equipment for making screens according to the process just described are well known to those skilled in the art. In a typical process, a low consistency dough is supplied from a pressurized upper box, which has an opening to provide a fine deposit of cellulose material on the Fourdrinier fabric to form a wet roll. The roll is then dehydrated to a fiber consistency of about 7% to about 25% (total weight of the canvas) through vacuum dehydration and subsequent drying by pressing operations in which the canvas is subjected to pressure developed by opposite mechanical members, for example, cylindrical rollers. The dehydrated roll is then pressed and dried by a steam drum apparatus known in the art as a Yankee dryer. The pressure can be developed in the Yankee dryer by mechanical means such as an opposite cylindrical drum pressing against the roller. Multiple Yankee dryers can be employed, where additional pressing is optionally employed between the drums. Molded sheets are considered to be compacted, since the entire roll is subjected to substantial mechanical compression forces while the fibers are moist, and then are dried while in a compressed state.
    [054] A particular embodiment of the present invention uses the UCTAD (uncrepe through-air-drying) technique to form the handkerchief product. Through the drying air you can increase the volume and smoothness of the roller. Examples of this technique are disclosed in U.S. Patent No. 5,048,589 to Cook, et al .; US Patent No. 5,399,412 to Sudall, et al .; US Patent No. 5,510,001 to Hermans, et al .; US Patent No. 5,591,309 to Ruqowski, et al .; US Patent No. 6,017,417 to Wendt, et al., U.S. Patent No. 6,432,270 to Liu, et al. The UCTAD drying technique generally involves the steps of: (1) forming a mass of cellulosic fibers, water and, optionally, other additives; (2) deposit the dough on a correct perforated conveyor, thus forming a fibrous roll on the perforated conveyor belt; (3) subject the fibrous roller to pass-through drying to remove water from the fibrous mass; and (4) removing the dry fibrous roller from the perforated conveyor belt.
    [055] Manufacturing
    [056] Conventional scalable methods, such as spraying, can be used to apply a superhydrophobic coating to a surface. In one embodiment, a hydrophilic nanostructured filler (Nanomer® PGV nano-clay from Sigma Aldrich), which is a bentonite clay without organic modification, is used. As a hydrophobic component, a 20% by weight dispersion of a fluorinated acrylic copolymer (PMC) in water is used, as obtained from DuPont (the trade name is Capstone® ST-100). The hydrophilic nano-clay is added to the water and sonicated until it produces a stable suspension. The sonication can be done through the use of a sonicator with probe at room temperature (Sonics®, 750 W, Ultrasonic High Intensity Processor, tip with diameter 13 mm at an amplitude of 30%). In these configurations, it can take about 15 to 30 min to form a suspension of nano-clay and water 15.5 g. The concentration of the nano-clay in water is kept below 2% by weight of the total suspension to prevent the formation of a gel, which makes the dispersion too viscous to spray. After placing the clay suspension in stable water under mechanical stirring at room temperature, the aqueous PMC dispersion is added dropwise to the suspension to produce a final spray dispersion. In such an embodiment, the concentration of each component in the final dispersion, to produce a hydrophobic coating, will be as follows: 95.5% by weight of water, 2.8% of PMC, 1.7% of nano-clay or 97 , 5% by weight of water, 1.25% of PMC, 1.25% of nanoclay. The coatings can be applied by spraying on cellulosic substrates, from a distance of about 15 to about 25 cm with an airbrush atomizer (Paasche VL feed trap, 0.55 mm Spray terminal) by hand or with the device assembly in an industrial fluid dispensing robot (EFD, TT Ultra Series). EFD nozzles with AIR AID can also be used to target extremely fine mists during spray application. The smallest nozzle diameter suggested for the EFD distribution system is around 0.35 mm. Air fans assist in the formation of the spray cone in an oval shape, which is useful for producing a uniform continuous coating on a substrate in linear motion. For the airbrush, the operation depends on the passage of air under pressure through the nozzle in order to feed the dispersion of particles through the bottom and also facilitate the atomization of the fluid at the nozzle outlet. The pressure drop applied through the sprayer can vary from about 2.1 to about 3.4 bar, depending on conditions.
    [057] Some technical difficulties are usually encountered when spraying water-based dispersions: The first major problem is insufficient fluid evaporation during atomization and a high degree of wetting of the dispersion on the coated substrate, resulting in irregular coatings due to contact with the pleat of the lining and the so-called "coffee stain effect" when the water eventually evaporates. The second major challenge is the relatively high surface tension of water, when compared to other solvents used for spray coating. Water, due to its high surface tension, tends to form non-uniform films in spray applications, thus requiring great care to ensure that a uniform layer is obtained. This is especially essential for hydrophobic substrates where water tends to drip and roll. It was observed that the best approach to apply aqueous dispersions of the present invention was to produce extremely fine droplets during spraying, and to apply only very thin coatings, so as not to saturate the substrate and reorient the hydrogen bond with the substrate that, after drying, it would make cellulosic substrates (for example paper towels) rigid.
    [058] In another embodiment, coatings are the spray applied first on a substrate, such as a standard cardboard or other cellulosic substrate; multiple spray passages are used to achieve different coating thicknesses. The pulverized films are then dried in an oven at about 80 ° C for about 30 min to remove all excess water. The size of the substrate can be, but is not limited to, about 7.5 cm x 9 cm. Once dry, the coatings are characterized for wettability (i.e., hydrophobic vs. hydrophilic). The substrates can be weighed in a microbalance (Sartorius® LE26P) before and after coating and drying, in order to determine the minimum level of coating necessary to induce superhydrophobicity. This "minimum coating" does not strictly mean that the sample will resist penetration by liquids, but that a drop of water will drip onto the surface and roll without any hindrance. The liquid repellency of the substrates, before and after coating, can be characterized by a hydrostatic pressure setting that determines the penetration pressures of the liquids (in centimeters of liquid).
    [059] Characterization of performance
    [060] The contact angle values can be obtained by a backlit optical image configuration using a CCD camera. For dynamic hysteresis measurements of the contact angle (which designates the self-cleaning property), the CCD camera can be replaced by a high-speed camera, such as the Redlake TM Motion Pro, in order to accurately capture the forward and reverse values the contact angle. The smaller the difference between the forward and reverse contact angles (ie hysteresis of the contact angle), the more self-cleaning a surface is. The liquid penetration pressure can be determined by increasing the hydrostatic pressure of the column until the liquid penetrates the sample, according to the ASTM F903-10 standard. The penetration of liquids can be recorded by an optical image configuration using a CCD camera.
    [061] The wettability of composite coatings can be tested on cardboard, a hydrophilic cellulosic substrate without texture considered representative of the general class of cellulosic substrates (textured or without texture). The concentration of nano-clay is constituted by the increase of the concentrations in the coating until the self-cleaning behavior is observed. The purpose of adding nano clay to the composite coating is to affect the texture of the coating. It is known that superhydrophobicity and self-cleaning behavior are controlled by two mechanisms, namely, surface roughness and surface energy. It has also been shown that hierarchical structures in conjunction with low-surface energy groups offer an excellent way to achieve the necessary roughness for super-hydrophobicity. The nano-clay has a platelet structure with nanometric thickness and microscale length that, when self-assembled (through electrostatic interaction), produces the aforementioned hierarchical structure. The concentration level of the nano clay in the composite coating where self-cleaning is first observed is about 38% by weight of the final composite coating (about 62% by weight of PCM of the final coating). When this composite coating is spray-melted onto the board, it can reach a contact angle of about 146 ± 3 ° (almost hydrophobic), and a contact angle hysteresis of about 21 ± 5 °. A lower hysteresis value can be expected for more hydrophobic nanostructured particles, but aqueous dispersions based on hydrophobic fillers are extremely difficult to obtain.
    [062] While in the case of superhydrophobicity, the emphasis is placed on increasing the roughness and decreasing the surface energy, to resist the penetration of liquids in the substrates, the pore size of the substrate and the surface energy are important factors. Figure 1 shows ideally a porous substrate configured (straight pores of uniform diameter and evenly distributed) resisting the penetration of water. In this configuration, the pressure required for the penetration of a hydrophobic substrate with pore size d is given by the Young-Laplace equation Δp = 4Ycosθ / d, where Y is the surface tension of the water, and θ (θ> 90 °) is the contact angle between the water and the substrate. The more hydrophobic the porous substrate (that is, the higher the value of θ), the greater the Δp of liquid penetration pressure. It is evident that the penetration of pressure increases inversely with the size of the pores (the thinner the pore, the greater the pressure necessary to cause the penetration of water). Although the pore size can be affected by applying relatively thick coating treatments (other hydrophobic formulations) to porous substrates, the effective pore size after coating is generally predetermined by the pore size of the substrate before applying the coating. The general purpose of applying the coating treatment is to decrease the surface energy of the substrate. In the case of a hydrophilic cellulose-based substrate, the coating treatment may not produce a uniform, low-surface energy film around some fibers, which, being hydrophilic, can also readily absorb water to result in a pressure value of 0 cm liquid penetration. The addition of coating treatments should provide some appreciable resistance to water penetration. The effectiveness of this approach is dictated by the liquid penetrating pressure (ie, "hydrostatic pressure", which is measured in centimeters of liquid used to challenge a surface). The higher this pressure is, the more effective the coating method is at transmitting hydrophobicity to the substrate. Naturally, the penetration pressure of the liquid depends on the liquid used (Y value in the Young-Laplace equation). Since alcohols have a lower surface tension than water, mixtures of water and alcohol result in lower penetration pressures. To show this, Fig. 2 shows penetration pressures of water liquids and mixture of water + IPA (9: 1 by weight). using only a coating by fluorochemical dispersion (PMC) and without nanostructured particles. Clearly, the penetration pressure of the IPA + water mixture for both samples is less than for water alone (as would be expected, due to the lower surface tension of the mixture).
    [063] Confocal microscopy observations can be made to determine the porosity of a porous substrate. Figure 3a shows a three-dimensional confocal image, while Figure 3b shows the data of the vacuum fraction, a meltblown hydrophobic substrate as a function of the depth of the substrate. The values of the vacuum fraction can be obtained from confocal images at different depths of the porous substrate. Confocal microscopy can also be performed on other substrates, but it has been determined that high density substrates can be very thick and densely packed to accurately determine their vacuum fraction. For a hydrophobic meltblown substrate, you can see with based on Fig. 3b that the vacuum fraction is at least close to the center of the substrate. In summary, Fig. 3 shows how it is possible to affect the vacuum fraction (and the resulting pore size) by applying a coating. Clearly, the coated substrate has a lower vacuum fraction, that is, smaller pores, which translates into the higher required penetration pressures.
    [064] EXAMPLES
    [065] The following are provided by way of example to facilitate the understanding of the invention and should not be construed to limit the invention to the examples.
    [066] Materials: Poly (vinylidene fluoride) pellets (PVDF) (Mw 530,000 Da) for NMP solution, PVDF powder (typical size 231 ± 66nm), ethyl 2-cyanoacrylate (ECA) monomer, trifluoroacetic acid (TFA), reagent grade ethanol, and N-methyl-2-pyrrolidone (NMP) were all obtained from Sigma Aldrich, USA. The particle filling material used was a nano-clay, namely Nanomer® 1.31PS, which is a surface-modified montmorillonite clay with 15-35% by weight of octadecylamine and 0.5-5% by weight of aminopropyltriethoxysilane, obtained from the Sigma Aldrich, USA. The aqueous fluorochemical dispersion, called PMC, has the trade name Capstone ST-100 (fluorinated acrylic copolymer, 20% by weight in water) and was obtained from DuPont.
    [067] Spray application: The coatings were sprayed onto the substrates with a single spray application at a fixed distance of 19 cm using an airbrush atomizer (Paasche VL siphon feed, 0.55 mm spray nozzle) mounted on a automated industrial application robot (EFD, Ultra TT Series). The coated substrates were dried for 30 minutes at 80 ° C in an oven, thus producing the coatings that were subjected to further structural characterization and wettability.
    [068] Composition of the Organic Baseline Composite Coating of Baseline (Formulation I): The dry composite coatings on the samples contain only PVDF, PMC and nano-clay.
    [069] Composition of the Aqueous Organic Compound Coating (Formulation II): The dry composite coatings on the samples contain only PVDF and PMC.
    [070] Coating Compositions Based on Pure Water (Formulations III, IV and V): The dry composite coatings on the samples contain only the fluorinated acrylic copolymer PMC (Form. III) and nano-clay (Form. IV and V).
    [071] Table 1 below shows the superhydrophobic formulations prepared using the materials described above.
    [072] Table 1: Superhydrophobic Composition of Five Formulations with Organic Solvent Content with Gradual Reduction

    a: The weight ratio of nano clay: (PMC + Nano clay) was 0.2, 0.4, 0.5, 0.6 and 0.8.
    [073] Formulations I-IV were sprayed onto cardboard substrates (standard cardboard used to manufacture shipping boxes) and water contact angles of the coated substrates were measured (see Fig. 4). Contact angle (CA) measurements were made on cardboard substrates, which have no inherent texture, thus allowing for accurate AC measurements.
    [074] Table 2 below shows the results of contact angle testing of Formulations I-IV applied to cardboard substrates (required for accurate AC measurements). Both water and water and alcohol (10% isopropanol) were used in the contact angle test.
    [075] Table 2: Contact angle data for I-IV Coating Formulations with two different Probe Liquids

    [076] Table 3 below shows the results of the contact angle test for the five cases of Formulation V applied on standard paper for photocopying without wood (High White brand). This paper was purchased from a wholesaler. It was manufactured in Brazil, with a size of 8.5 inches by 11 inches, base weight of about 78 grams per square meter. The data indicates that a hydrophobic coating (i.e., CA> 150 degrees) is obtained in a nano-clay / solids weight ratio of 0.4. When this proportion exceeds 0.5, a dramatic reduction in AC is observed.
    [077] Table 3: Water Contact Angle Data for Formulation V Applied on Standard Photocopy Paper

    [078] Table 4 below lists five Kimberly-Clark® substrate materials used in spray experiments.
    [079] Table 4: Kimberly-Clark® Substrate Materials

    [080] Confocal microscopy was used to measure porosity and to characterize uncoated and coated samples of all substrate materials before coating. Only Formulation I was applied to all substrates for subsequent characterization by confocal microscopy.
    [081] Test Method Descriptions: 1. Confocal microscopy: In order to facilitate the creation of images by the confocal microscope (Zeiss LSM 510), all samples were coated with a fluorescent dye (Rhodamine 610). The coating was done by dissolving the dye in water, immersing the sample in the dye solution, and allowing the sample to dry under ambient conditions. By using the "coffee stain" effect, uniform dye deposition can be obtained on the substrate to be worked. The porosity of the substrate (or fraction of void) was measured by importing stacks of confocal images into Matlab and analysis by means of standard image analysis and material volume reconstruction technique. The images were subjected to the threshold and then were characterized for the vacuum fraction by counting empty pixel areas (that is, porosity) as a function of depth in the substrate.2. Liquid Penetration Pressure: Liquid penetration measurements were made in accordance with ASTM F903-10.
    [082] Results:
    [083] Figures 3b-d show the void fraction of the substrate and the directional depth z of the Kimberly-Clark® Towel Paper coated in SMS, spunbond, before and after the application of Formulation I at a rate of 27.4 g / m2. (Fig. 3b shows the void fraction of the SMS substrate before and after the application of Formulation I. Figure 3c shows the void fraction of the spunbond substrate before and after the application of Formulation I. Figure 3d shows the void fraction of substrate of Kimberly-Clark® Towel Paper before and after the application of Formulation I).
    [084] Figure 5 shows the hydrostatic pressure of the five samples referred to in Table 4, after being coated with Formulation I. As shown, Figure 5a shows the coating effect at 13.7 g / m2 while Figure 5b shows the effect of the coating at 27.4 g / m2.
    [085] Figure 6a shows the effect of the base coating level on the water and water + alcohol hydrostatic pressure heights of the SMS (Sample 1) and Figure 6b shows the surface of the Kimberly-Clark® Towel Paper (Example 4) coated with Formulation I. Each of these tests was performed with the two test liquids. Figure 7 shows the effect of Formulation II on the hydrostatic pressure of water and water-alcohol of the coated SMS (Sample 1), and the Kimberly-Clark® Towel Paper (Sample 4). The two samples were coated with Formulation II at a rate of 78.4 g / m2.
    [086] Figure 8 shows the effect of Formulation III on the hydrostatic pressure of water and water-alcohol of the coated SMS (Sample 1) and Kimberly-Clark® Towel Paper (Sample 4). The two samples were coated with Formulation III at a rate of 47 g / m2.
    [087] Fig. 9 shows the effect of Formulations I-III and V on the height of hydrostatic water pressure of the coated SMS (Sample 1) and Kimberly-Clark® Towel Paper (Sample 4). Note that the level of coating applied in these tests was the minimum so that the accumulation of water could be reached. For Formulations I and V in Example 4, no hydrostatic pressure was sustainable (i.e., water penetrated the coated substrate even under zero pressure applied). In this particular case, the coating levels of Sample 1 were in the range 0.78-1.1 g / m2, while for Sample 4 they were in the range of 1.43-1.65 g / m2 (the variability due to non-uniformity of the substrate). These coatings were much thinner than those examined in Figure 5, where higher hydrostatic pressures were obtained for both samples (1 and 4).
    [088] All documents cited herein are, to the relevant extent, incorporated herein by reference; the citation of any document is not to be interpreted as an admission that it is the prior state of the art in relation to the present invention. To the extent that any meaning or definition of a term in this document conflicts with the meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall prevail.
    [089] While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is intended, therefore, to cover in the appended claims all such changes and modifications that are within the scope of the present invention
    权利要求:
    Claims (12)
    [0001]
    1. A super-hydrophobic surface, characterized by the fact that it comprises a substrate treated with a composition that comprises: a. a hydrophobic component, in which the hydrophobic component is a water-dispersible hydrophobic polymer modified by the introduction of a comonomer in its molecular structure and is selected from the group consisting of fluorinated polymers, perfluorinated polymers and mixtures thereof; b. hydrophilic nanostructured particles; ec. water, in which the composition is free of organic solvent; wherein the hydrophobic component and the nanostructured particles are present in an amount of 1.0% to 3.0%, by weight of the dispersion; wherein the weight ratio of the hydrophobic component to the nanostructured particle is 1: 1 to 4: 1; and in which water is present in an amount of 95% to 99%, by weight of the composition.
    [0002]
    2. The super-hydrophobic surface according to claim 1, characterized by the fact that the nanostructured particles are selected from the group consisting of smoked silica, hydrophobic titania treated by surfactant, zinc oxide, nano clay and mixtures thereof.
    [0003]
    The superhydrophobic surface according to claim 1, characterized by the fact that it also comprises a surfactant from 0% to 3%, by weight of the composition.
    [0004]
    4. The superhydrophobic surface according to claim 3, characterized by the fact that surfactants are selected from nonionic, cationic or anionic surfactants.
    [0005]
    5. The super-hydrophobic surface according to claim 1, characterized by the fact that the water-dispersible hydrophobic polymer comprises a comonomer selected from acrylic monomers and acrylic precursors.
    [0006]
    The superhydrophobic surface according to claim 1, characterized by the fact that it also comprises a binder from 0% to 2.0%, by weight of the composition.
    [0007]
    7. The super-hydrophobic surface according to claim 1, characterized by the fact that it further comprises a stabilizing agent selected from the group comprising long-chain fatty acids, long-chain fatty acid salts, ethylene-acrylic acid, copolymers ethylene-methacrylic acid, sulfonic acid, acetic acid and the like.
    [0008]
    8. The super-hydrophobic surface according to claim 1, characterized by the fact that it also comprises a filler selected from the group comprising ground glass, calcium carbonate, aluminum trihydrate, talc, antimony trioxide, fly ash and clays .
    [0009]
    The superhydrophobic surface according to claim 8, characterized in that the filler is present in an amount of 0.01 to 600 parts, by weight of the hydrophobic component.
    [0010]
    10. The superhydrophobic surface according to claim 1, characterized by the fact that the composition is dispersed by means of spraying.
    [0011]
    11. The super-hydrophobic surface according to claim 1, characterized by the fact that the surface is a non-woven blanket.
    [0012]
    12. The superhydrophobic surface according to claim 1, characterized by the fact that the surface is a tissue paper product.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112014000770B1|2021-03-16|super-hydrophobic surfaces
    US9803100B2|2017-10-31|Non-fluorinated water-based superhydrophobic surfaces
    US10005917B2|2018-06-26|Non-fluorinated water-based superhydrophobic compositions
    US20180030282A1|2018-02-01|Non-fluorinated water-based superhydrophobic surfaces
    CN106062449B|2019-05-10|Check valve non-woven material
    US9217094B2|2015-12-22|Superhydrophobic compositions
    US10533096B2|2020-01-14|Non-fluorinated water-based superhydrophobic compositions
    BR112020002769A2|2020-07-28|non-fluorinated composition
    US10865317B2|2020-12-15|Low-fluorine compositions with cellulose for generating superhydrophobic surfaces
    RU2747809C2|2021-05-14|Wetting structuring method and models for pump-free transfer and precise volume control of liquids on and through porous materials
    US20150315749A1|2015-11-05|Hydrophobic treatment on hydrophilic nonwoven
    US20150275419A1|2015-10-01|Tissue-based water barrier material
    BR112020003159A2|2020-09-15|superhydrophobic surface, and disposable absorbent article.
    KR20190090798A|2019-08-02|Methods and apparatus for moving and dispensing aqueous liquids at high speeds on porous, nonwoven substrates
    同族专利:
    公开号 | 公开日
    EP2736985A4|2015-04-22|
    BR112014000770A2|2017-07-04|
    AU2012288560A1|2014-01-16|
    US9364859B2|2016-06-14|
    EP2736985A2|2014-06-04|
    KR20140053127A|2014-05-07|
    MX342401B|2016-09-27|
    WO2013014546A3|2013-04-11|
    AU2012288560B2|2015-09-17|
    WO2013014546A2|2013-01-31|
    MX2014000694A|2014-02-27|
    RU2014103338A|2015-09-10|
    US20130029551A1|2013-01-31|
    EP2736985B1|2017-10-11|
    CN103687916A|2014-03-26|
    KR101702190B1|2017-02-03|
    RU2601339C2|2016-11-10|
    CN103687916B|2017-01-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3338992A|1959-12-15|1967-08-29|Du Pont|Process for forming non-woven filamentary structures from fiber-forming synthetic organic polymers|
    US3502763A|1962-02-03|1970-03-24|Freudenberg Carl Kg|Process of producing non-woven fabric fleece|
    US3341394A|1966-12-21|1967-09-12|Du Pont|Sheets of randomly distributed continuous filaments|
    US3494821A|1967-01-06|1970-02-10|Du Pont|Patterned nonwoven fabric of hydraulically entangled textile fibers and reinforcing fibers|
    GB1215861A|1967-02-09|1970-12-16|Minnesota Mining & Mfg|Cleanable stain-resistant fabrics or fibers and polymers therefor|
    US3542615A|1967-06-16|1970-11-24|Monsanto Co|Process for producing a nylon non-woven fabric|
    US3849241A|1968-12-23|1974-11-19|Exxon Research Engineering Co|Non-woven mats by melt blowing|
    DE2048006B2|1969-10-01|1980-10-30|Asahi Kasei Kogyo K.K., Osaka |Method and device for producing a wide nonwoven web|
    DE1950669C3|1969-10-08|1982-05-13|Metallgesellschaft Ag, 6000 Frankfurt|Process for the manufacture of nonwovens|
    US3645990A|1970-01-29|1972-02-29|Du Pont|Fluorinated oil- and water-repellent and dry soil resistant polymers|
    CA948388A|1970-02-27|1974-06-04|Paul B. Hansen|Pattern bonded continuous filament web|
    DE2437395C3|1973-10-15|1979-02-08|E.I. Du Pont De Nemours And Co., Wilmington, Del. |Film made from fluorine-containing polymers with side chains containing sulfonyl groups|
    US4100324A|1974-03-26|1978-07-11|Kimberly-Clark Corporation|Nonwoven fabric and method of producing same|
    GB1550955A|1975-12-29|1979-08-22|Johnson & Johnson|Textile fabric and method of manufacturing the same|
    US4340563A|1980-05-05|1982-07-20|Kimberly-Clark Corporation|Method for forming nonwoven webs|
    US4659609A|1986-05-02|1987-04-21|Kimberly-Clark Corporation|Abrasive web and method of making same|
    US4833003A|1986-08-15|1989-05-23|Kimberly-Clark Corporation|Uniformly moist abrasive wipes|
    US5048589A|1988-05-18|1991-09-17|Kimberly-Clark Corporation|Non-creped hand or wiper towel|
    JP2682130B2|1989-04-25|1997-11-26|三井石油化学工業株式会社|Flexible long-fiber non-woven fabric|
    US5108827A|1989-04-28|1992-04-28|Fiberweb North America, Inc.|Strong nonwoven fabrics from engineered multiconstituent fibers|
    CA2048905C|1990-12-21|1998-08-11|Cherie H. Everhart|High pulp content nonwoven composite fabric|
    US5382400A|1992-08-21|1995-01-17|Kimberly-Clark Corporation|Nonwoven multicomponent polymeric fabric and method for making same|
    US5336552A|1992-08-26|1994-08-09|Kimberly-Clark Corporation|Nonwoven fabric made with multicomponent polymeric strands including a blend of polyolefin and ethylene alkyl acrylate copolymer|
    US5350624A|1992-10-05|1994-09-27|Kimberly-Clark Corporation|Abrasion resistant fibrous nonwoven composite structure|
    US5399412A|1993-05-21|1995-03-21|Kimberly-Clark Corporation|Uncreped throughdried towels and wipers having high strength and absorbency|
    US5411636A|1993-05-21|1995-05-02|Kimberly-Clark|Method for increasing the internal bulk of wet-pressed tissue|
    US6093665A|1993-09-30|2000-07-25|Kimberly-Clark Worldwide, Inc.|Pattern bonded nonwoven fabrics|
    CA2123330C|1993-12-23|2004-08-31|Ruth Lisa Levy|Ribbed clothlike nonwoven fabric and process for making same|
    CA2142805C|1994-04-12|1999-06-01|Greg Arthur Wendt|Method of making soft tissue products|
    US5468598A|1994-04-18|1995-11-21|Eastman Kodak Company|Solid particle dispersions for imaging systems|
    US5591309A|1995-02-06|1997-01-07|Kimberly-Clark Corporation|Papermaking machine for making uncreped throughdried tissue sheets|
    US5539021A|1995-06-05|1996-07-23|The Dow Chemical Company|Process for preparing high internal phase ratio emulsions and latexes derived thereof|
    US5759926A|1995-06-07|1998-06-02|Kimberly-Clark Worldwide, Inc.|Fine denier fibers and fabrics made therefrom|
    EP0864006B1|1995-11-30|2003-02-19|Kimberly-Clark Worldwide, Inc.|Superfine microfiber nonwoven web|
    USD390708S|1996-10-31|1998-02-17|Kimberly-Clark Worldwide, Inc.|Pattern for a bonded fabric|
    US6200669B1|1996-11-26|2001-03-13|Kimberly-Clark Worldwide, Inc.|Entangled nonwoven fabrics and methods for forming the same|
    US5962112A|1996-12-19|1999-10-05|Kimberly-Clark Worldwide, Inc.|Wipers comprising point unbonded webs|
    DE19726802C1|1997-06-24|1998-06-10|Dyneon Gmbh|Aqueous dispersion of different fluoro-polymers giving compact, thick film with high dielectric strength|
    AU8699198A|1997-08-15|1999-03-08|Dow Chemical Company, The|High internal phase emulsions and porous materials prepared therefrom|
    US6315864B2|1997-10-30|2001-11-13|Kimberly-Clark Worldwide, Inc.|Cloth-like base sheet and method for making the same|
    US6197404B1|1997-10-31|2001-03-06|Kimberly-Clark Worldwide, Inc.|Creped nonwoven materials|
    US6103061A|1998-07-07|2000-08-15|Kimberly-Clark Worldwide, Inc.|Soft, strong hydraulically entangled nonwoven composite material and method for making the same|
    USD428267S|1999-08-27|2000-07-18|Kimberly-Clark Worldwide, Inc.|Repeating pattern for a bonded fabric|
    BR0116842A|2001-01-30|2003-12-16|Procter & Gamble|Hard surface modification coatings and application processes|
    US20020045010A1|2000-06-14|2002-04-18|The Procter & Gamble Company|Coating compositions for modifying hard surfaces|
    CA2321345A1|2000-10-02|2002-04-02|Abdelbast Guerfi|Use of graphite in a composite to reduce ice accretion|
    US6432270B1|2001-02-20|2002-08-13|Kimberly-Clark Worldwide, Inc.|Soft absorbent tissue|
    KR20040044531A|2001-09-05|2004-05-28|쓰리엠 이노베이티브 프로퍼티즈 캄파니|Fluoropolymer dispersion containing no or little low molecular weight fluorinated surfactant|
    DE10231757A1|2002-07-13|2004-01-22|Creavis Gesellschaft Für Technologie Und Innovation Mbh|Process for the preparation of a surfactant-free suspension on an aqueous basis of nanostructured, hydrophobic particles and their use|
    CN1820058A|2003-05-20|2006-08-16|帝斯曼知识产权资产管理有限公司|Hydrophobic coatings comprising reactive nano-particles|
    CN1826391B|2003-06-23|2012-12-12|苏黎世大学|Superhydrophobic coating|
    US7803865B2|2003-08-25|2010-09-28|Dow Global Technologies Inc.|Aqueous dispersion, its production method, and its use|
    FR2862235B1|2003-11-13|2007-12-28|Rhodia Chimie Sa|EMULSION FOR VEHICULATING HYDROPHOBIC ACTIVE MATERIAL TO AQUEOUS SUBSTRATE|
    US20050229327A1|2004-04-20|2005-10-20|Casella Victor M|Fabric treatment for stain release|
    US7722951B2|2004-10-15|2010-05-25|Georgia Tech Research Corporation|Insulator coating and method for forming same|
    DE102004062742A1|2004-12-27|2006-07-06|Degussa Ag|Textile substrates with self-cleaning properties |
    US20070027232A1|2005-07-27|2007-02-01|Chemcoat, Inc.|Coating compositions incorporating nanotechnology and methods for making same|
    DE102005051550A1|2005-10-27|2007-05-03|Fibertex A/S|Superhydrophobic coating of a polymer fleece, in particular a polypropylene fleece|
    US8067065B2|2005-12-08|2011-11-29|Toyota Motor Engineering & Manufacturing North America, Inc.|Fibrillar, nanotextured coating and method for its manufacture|
    US20080221009A1|2006-01-30|2008-09-11|Subbareddy Kanagasabapathy|Hydrophobic self-cleaning coating compositions|
    CN100384785C|2006-03-28|2008-04-30|何安荣|Water type multi-functional, hydrophobic, air-permeability and porous material, prepn. method and application thereof|
    US20080015298A1|2006-07-17|2008-01-17|Mingna Xiong|Superhydrophobic coating composition and coated articles obtained therefrom|
    US8202614B2|2006-08-09|2012-06-19|Luna Innovations Incorporated|Additive particles having superhydrophobic characteristics and coatings and methods of making and using the same|
    US20080221263A1|2006-08-31|2008-09-11|Subbareddy Kanagasabapathy|Coating compositions for producing transparent super-hydrophobic surfaces|
    US7803499B2|2006-10-31|2010-09-28|Gm Global Technology Operations, Inc.|Super-hydrophobic composite bipolar plate|
    CN101557784B|2006-12-11|2014-12-10|Sca卫生用品公司|Absorbent article with a strongly hydrophobic layer|
    US20080153963A1|2006-12-22|2008-06-26|3M Innovative Properties Company|Method for making a dispersion|
    KR100823895B1|2006-12-27|2008-04-21|한국과학기술원|Superhydrophobic coating film comprising inorganic particles having different diameters, coating composition, and the forming method of coating film|
    US7943234B2|2007-02-27|2011-05-17|Innovative Surface Technology, Inc.|Nanotextured super or ultra hydrophobic coatings|
    US7732497B2|2007-04-02|2010-06-08|The Clorox Company|Colloidal particles for lotus effect|
    US20080245273A1|2007-04-05|2008-10-09|Jouko Vyorkka|Hydrophobic coatings|
    US20080250978A1|2007-04-13|2008-10-16|Baumgart Richard J|Hydrophobic self-cleaning coating composition|
    US20090107524A1|2007-09-27|2009-04-30|Cognis Ip Management Gmbh|Surface-Modification Compositions|
    US9993403B2|2007-12-20|2018-06-12|Avon Products, Inc.|Cosmetic compositions for imparting superhydrophobic films|
    CN101952326A|2008-01-22|2011-01-19|陶氏环球技术公司|Hydrophobic coating|
    CN101250597B|2008-03-13|2012-05-09|陕西科技大学|Preparation method of nano self-cleaning leather or product|
    CN101544476A|2008-03-28|2009-09-30|皮尔金顿集团有限公司|Super-hydrophobic transparent coating and preparation method thereof|
    KR20110042268A|2008-06-30|2011-04-26|에스티씨. 유엔엠|A superhydrophobic aerogel that does not require per-fluoro compounds or contain any fluorine|
    CN101307210B|2008-07-02|2010-10-13|胡硕|Ultra-discharging water-soluble fluor-silicon-acrylic coatings with nano particles|
    WO2010017558A2|2008-08-08|2010-02-11|The Board Of Trustees Of The University Of Illinois|Composite material compositions and methods|
    US20100136335A1|2008-10-02|2010-06-03|Sargent Ralph R|Compositions and methods for treating textile fibers|
    US20100092809A1|2008-10-10|2010-04-15|Board Of Trustees Of Michigan State University|Electrically conductive, optically transparent films of exfoliated graphite nanoparticles and methods of making the same|
    CN101434802B|2008-12-19|2011-10-26|天津工业大学|Water system super-hydrophobic surface coating agent and preparation thereof|
    JP4790003B2|2008-12-26|2011-10-12|株式会社カーメイト|Coating film forming method and coating liquid|
    US9062219B2|2009-01-21|2015-06-23|Xerox Corporation|Superhydrophobic nano-fabrics and coatings|
    RU2400510C1|2009-04-21|2010-09-27|Учреждение Российской академии наук Институт физической химии и электрохимии им. А.Н. Фрумкина РАН |Composition for preparing super-hydrophobic coating|
    CN102597067A|2009-08-19|2012-07-18|荷兰联合利华有限公司|Ultrahydrophobic coating and method for making the same|
    WO2011053904A1|2009-10-30|2011-05-05|Dow Global Technologies Inc.|Alkyd dispersion, and a process for producing the same|
    KR101126256B1|2009-11-27|2012-03-19|부산대학교 산학협력단|Superhydrophobic coating composition, Superhydrophobic coating film using the same, and Method of manufacturing thereof|
    ES2749998T3|2009-12-10|2020-03-24|Invista Textiles Uk Ltd|Use of aqueous dirt repellent dispersions, soft dirt repellent articles, and methods of making them|
    CN101845242A|2010-04-28|2010-09-29|四川大学|Super-hydrophobic nano-composite coating and preparation method thereof|
    US8486319B2|2010-05-24|2013-07-16|Integran Technologies Inc.|Articles with super-hydrophobic and/or self-cleaning surfaces and method of making same|
    KR101252224B1|2011-09-16|2013-04-05|울산대학교 산학협력단|modified graphene and nano- composite material containing the same|EP3406353B1|2013-03-15|2021-02-24|Liquiglide Inc.|Methods for liquid-impregnated surfaces with enhanced durability|
    EP3063443A4|2013-10-31|2017-06-14|Kimberly-Clark Worldwide, Inc.|One-way valve nonwoven material|
    WO2015148661A1|2014-03-25|2015-10-01|Varanasi Kripa K|Spray processes and methods for forming liquid-impregnated surfaces|
    US20150275419A1|2014-03-31|2015-10-01|Kimberly-Clark Worldwide, Inc.|Tissue-based water barrier material|
    US20150315749A1|2014-05-02|2015-11-05|Kimberly-Clark Worldwide, Inc.|Hydrophobic treatment on hydrophilic nonwoven|
    CN104532664B|2014-11-27|2017-02-01|安徽理工大学|Universal preparation method for self-cleaning superhydrophobic paper|
    US10533096B2|2015-02-27|2020-01-14|Kimberly-Clark Worldwide, Inc.|Non-fluorinated water-based superhydrophobic compositions|
    WO2016138277A1|2015-02-27|2016-09-01|Kimberly-Clark Worldwide, Inc.|Non-fluorinated water-based superhydrophobic surfaces|
    CN104846508B|2015-06-15|2017-07-04|湖州市菱湖重兆金辉丝织厂|A kind of hydrophobic fabric of the imitative boar cage grass structure in surface|
    CN105056901B|2015-07-31|2017-05-24|东北林业大学|Superhydrophobic and super-oleophilic adsorbent with straw as raw material and preparation method thereof|
    US10144815B2|2015-09-29|2018-12-04|Portland State University|Modified nano-clays and coating compositions including the same|
    EP3362599A4|2015-10-14|2019-05-29|HeiQ Pty Ltd|Process for providing water repellency|
    CN108660760B|2017-04-01|2020-10-20|江苏纳纤新材料科技有限公司|Warm-keeping moisture-resistant self-cleaning scarf and preparation method thereof|
    CN110799162A|2017-06-30|2020-02-14|宝洁公司|Disposable absorbent article with surface modified topsheet|
    US10865317B2|2017-08-31|2020-12-15|Kimberly-Clark Worldwide, Inc.|Low-fluorine compositions with cellulose for generating superhydrophobic surfaces|
    US20200346869A1|2017-11-15|2020-11-05|Laitram, L.L.C.|Superhydrophobic plastic conveyor components and methods for their molding|
    CN108649192B|2018-04-08|2019-08-16|河南大学|A method of the uniform decorative layer of electrode material surface is prepared based on contact angle test|
    EP3829509A1|2018-08-03|2021-06-09|The Procter & Gamble Company|Webs with compositions applied thereto|
    KR102177314B1|2018-09-28|2020-11-10|한밭대학교 산학협력단|Superhydrophobic - superoleophilic nickel foams and method for making same|
    CN109338737B|2018-10-10|2021-05-25|五邑大学|Hydrophobic fabric finishing agent, preparation method of hydrophobic fabric, hydrophobic fabric and application of hydrophobic fabric|
    CN109468156B|2018-11-02|2021-09-10|山西大学|Easy-demoulding coating for pouring mould and coating method thereof|
    EP3670740B1|2018-12-20|2022-02-02|European Central Bank|Amphiphobic cellulosic materials, production thereof and uses|
    CN111607902A|2020-04-30|2020-09-01|广东顺事德智能科技有限公司|Hydrophobic melt-blown fabric with rough surface and preparation method thereof|
    CN113521882A|2021-07-06|2021-10-22|哈尔滨工业大学|Dust-free paper-based flexible water treatment material and preparation method thereof|
    法律状态:
    2017-07-11| B15I| Others concerning applications: loss of priority|Free format text: PERDA DA PRIORIDADE US13/193,065, REIVINDICADA NO PCT/IB2012/053062, CONFORME AS DISPOSICOES PREVISTAS NA LEI 9279, DE 14/05/1996 (LPI), ART. 16,7O, ITEM 28, DO ATO NORMATIVO 128/97, E NO ART. 29 DA RESOLUCAO INPI-PR 77/2013. ESTA PERDA SE DEU PELO FATO DE O DEPOSITANTE CONSTANTE DA PETICAO DE REQUERIMENTO DO REFERIDO PEDIDO PCT SER DISTINTO DAQUELE QUE DEPOSITOU A PRIORIDADE REIVINDICADA E NAO TER SIDO APRESENTADO DOCUMENTO COMPROBATORIO DE CESSAO, CONFORME AS DISPOSICOES PREVISTAS NA LEI 9279 DE 14/05/1996 (LPI), ART. 16,6O, ITEM 27, DO ATO NORMATIVO 128/97, E NO ART. 2 DA RESOLUCAO INPI-PR 179/2017. |
    2017-09-19| B12F| Appeal: other appeals|
    2018-03-27| B15K| Others concerning applications: alteration of classification|Ipc: B05D 5/08 (2006.01), B32B 5/02 (2006.01), B32B 27/ |
    2019-10-08| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2021-02-02| B09A| Decision: intention to grant|
    2021-03-16| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 18/06/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/193,065|US9364859B2|2011-07-28|2011-07-28|Superhydrophobic surfaces|
    US13/193,065|2011-07-28|
    PCT/IB2012/053062|WO2013014546A2|2011-07-28|2012-06-18|Superhydrophobic surfaces|
    [返回顶部]